Organometallic monoacylalkylphosphines

ABSTRACT

Compounds of the formula I                    
     Ar is a group                    
     or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R 1  and R 2  are C 1 -C 20 alkyl, OR 11 , CF 3  or halogen; R 3 , R 4  and R 5  are hydrogen, C 1 -C 20 alkyl, OR 11  or halogen; R 6  is unsubstituted or substituted C 1 -C 24 alkyl, C 2 -C 24 alkyl, which is interrupted by O, S or NR 14  and is unsubstituted or substituted; C 2 -C 24 alkenyl, uninterrupted or interrupted by O, S or NR 14  and unsubstituted or substituted; unsubstituted or substituted C 7 -C 24 arylalkyl; C 4 -C 24 cycloalkyl, uninterrupted or interrupted by O, S and/or NR 14 ; or C 8 -C 24 arylcycloalkyl; R 11  is C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl, phenyl, benzyl or C 2 -C 20 alkyl, interrupted by O or S and unsubstituted or substituted; R 12  and R 13  are hydrogen, C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl, phenyl, benzyl or C 2 -C 20 alkyl, interrupted by O atoms and unsubstituted or substituted; or R 12  and R 13  together are C 3 -C 5 alkylene, uninterrupted or interrupted by O, S or NR 14 ; R 14  is hydrogen, phenyl, C 1 -C 12 alkyl or C 2 -C 12 alkyl, interrupted by O or S and unsubstituted or substituted; and M is hydrogen, Li, Na or K; are valuable intermediates for the preparation of unsymmetrical bisacylphosphine oxides and monoacylphosphine oxides.

The present application relates to organometallicmonoacylalkylphosphines, to the preparation thereof, and to the usethereof as starting materials for the preparation of unsymmetrical mono-and bisacylphosphines, -phosphine oxides or sulfides.

Various metalated phosphines have become known as intermediates in thepreparation of a-cylphosphine oxides. Thus, for example in EP 40721,acylphosphines are obtained by reaction of acyl halides with metalateddiorganophosphines or silylated phosphines or diorganophosphines.

By oxidation of the acyldiorganophosphines, the correspondingacylphosphine oxide photoinitiators can be prepared therefrom. WO00/32612 discloses a one-pot process for the preparation ofbisacylphosphine oxides in which dichloroorganophosphines are metalated,then reacted with acyl halides to give the corresponding acylphosphinesand then, by oxidation or sulfurization, the bisacylphosphine oxides orsulfides are obtained.

Alkylacylphosphines and the corresponding metalated compounds are notknown in the prior

U.S. Pat. No. 5,399,770 discloses a bisacylphosphine oxide having twodifferent acyl groups, and U.S. Pat. No. 5,218,009 specificallydiscloses a monoacylphosphine oxide having two different non-acylsubstituents on the phosphorus atom.

For the technology, readily accessible starting materials for thepreparation of acylphosphine oxides and sulfides are of greatimportance. Of particular interest are starting materials which permitthe preparation of “unsymmetrical” bisacylphosphine oxides and sulfides,i.e. those with two different acyl groups, in a simple manner.

A process for the preparation of metalated alkylacylphosphines which aresuitable as starting materials for the preparation of acylphosphineoxide or acylphosphine sulfide photoinitiators has been found. Themajority of the phosphines, phosphine oxides and phosphine sulfidesobtained are novel.

The invention provides compounds of the formula I

in which Ar is a group

or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy;

R₁ and R₂ independently of one another are C₁-C₂₀alkyl, OR₁₁, CF₃ orhalogen;

R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₂₀alkyl,OR₁₁ or halogen; or in each case two of the radicals R₁, R₂, R₃, R₄ andR₅ together form C₁-C₂₀alkylene, which can be interrupted by O, S orNR₁₄;

R₆ is C₁-C₂₄alkyl, unsubstituted or substituted by cycloalkenyl, phenyl,CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁,N(R₁₄)C(O)N(R₁₄), OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁,SR₁₁, N(R₁₂)(R₁₃) or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₅-C₂₄cycloalkenyl which is uninterrupted or interrupted once or morethan once by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₇-C₂₄arylalkyl which is unsubstituted or substituted on the aryl groupby C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen;

C₄-C₂₄cycloalkyl which is uninterrupted or interrupted once or more thanonce by O, S and/or NR₁₄ and which is unsubstituted or substituted byOR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

or C₈-C₂₄arylcycloalkyl or C₈-C₂₄arylcycloalkenyl;

R₁₁ is H, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl orC₂-C₂₀alkyl which is interrupted once or more than once by O or S andwhich is unsubstituted or is substituted by OH and/or SH;

R₁₂ and R₁₃ independently of one another are hydrogen, C₁-C₂₀alkyl,C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl which is interrupted onceor more than once by nonconsecutive O atoms and which is unsubstitutedor substituted by OH and/or SH; or R₁₂ and R₁₃ together areC₃-C₅alkylene which is uninterrupted or interrupted by O, S or NR₁₄;

R₁₄ is hydrogen, phenyl, C₁-C₁₂alkyl or C₂-C₁₂alkyl which is interruptedonce or more than once by O or S and which is unsubstituted orsubstituted by OH and/or SH; and

M is hydrogen, Li, Na or K.

C₁-C₂₄Alkyl is linear or branched and is, for example, C₂-C₂₄alkyl,C₁-C₂₀alkyl, C₁-C₁₈alkyl, C₁-C₁₂alkyl, C₁-C₈alkyl, C₁-C₆alkyl orC₁-C₄alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl,2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl,dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl, icosyl or tetraicosyl.

For example, R₁, R₂, R₃, R₁′, R₂′ and R₃′ are C₁-C₈alkyl, in particularC₁-C₆alkyl, preferably C₁-C₄alkyl, particularly preferably methyl.

C₁-C₂₀Alkyl, C₁-C₁₈alkyl, C₁-C₁₂alkyl, C₁-C₆alkyl and C₁-C₄alkyl arelikewise linear or branched and have, for example, the meanings givenabove apart from the corresponding number of carbon atoms.

R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are,for example, C₁-C₈alkyl, in particular C₁-C₆alkyl, preferablyC₁-C₄alkyl, for example methyl or butyl.

C₂-C₂₄Alkyl which is interrupted once or more than once by O, S or NR₁₄is, for example, interrupted 1-9 times, e.g. 1-7 times or once or twice,by O, S or NR₁₄. If the radicals are interrupted by two or more O, S orNR₁₄, then the O atoms, S atoms or NR₁₄ groups are in each caseseparated from one another by at least one methylene group. The O atoms,S atoms or NR₁₄ groups are thus not directly consecutive. The alkylradical can be linear or branched. For example, structural units such as—CH₂—O—CH₃, —CH₂CH₂—O—CH₂CH₃, —[CH₂CH₂O], —CH₃, where z=1 to 9,—(CH₂CH₂O)₇CH₂CH₃, —CH₂—CH(CH₃)—O—CH₂—CH₂CH₃, —CH₂—CH(CH₃)—O—CH₂—CH₃,—CH₂SCH₃ or —CH₂—N(CH₃)₂ arise.

C₂-C₂₀Alkyl, C₂-C₁₈alkyl, C₂-C₁₂alkyl which are interrupted by O andoptionally by S are likewise linear or branched and can, for example,have the meanings given above apart from the given number of carbonatoms. The O atoms are not consecutive here either.

C₁-C₁₈Haloalkyl is C₁-C₁₈alkyl as described above which is mono- orpolysubstituted by halogen. This is, for example, perfluorinatedC₁-C₁₈alkyl. Examples are chloromethyl, trichloromethyl, trifluoromethylor 2-bromopropyl, in particular trifluoromethyl or trichloromethyl.

C₃-C₂₄Cycloalkyl, e.g. C₄-C₂₄cycloalkyl, C₅-C₁₂cycloalkyl,C₄-C₁₂cycloalkyl, C₃-C₁₂cycloalkyl, C₃-C₈cycloalkyl, stands both forindividual alkyl ring systems and also bridged alkyl ring systems.Furthermore, the radicals can also contain linear or branched alkylgroups (as described above apart from the corresponding number of carbonatoms). Examples are cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl,cyclododecyl, cycloicosyl, in particular cyclopentyl and cyclohexyl,preferably cyclohexyl. Further examples are

C₃-C₈Cycloalkyl, e.g. C₃-C₆cycloalkyl, can have the meanings given aboveapart from the corresponding number of carbon atoms.

C₃-C₁₈Cycloalkyl substituted by C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen ispreferably substituted in both ortho positions of the cycloalkyl ring.Preference is given to 2,4,6-trimethylcyclohexyl and2,6-dimethoxycyclohexyl.

C₂-C₂₄Alkenyl radicals are mono- or polyunsaturated, and are linear orbranched and are, for example, C₂-C₁₈alkenyl, C₂-C₈alkenyl, C₂-C₆alkenylor C₂-C₄alkenyl. Examples are vinyl, allyl, methallyl,1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl,1-octenyl, decenyl or dodecenyl, in particular allyl. C₂-C₁₈Alkenyl hasthe same meanings as given above apart from the corresponding number ofcarbon atoms.

If C₂-C₂₄alkenyl radicals are interrupted, for example, by O, then thefollowing structures are, for example, included:—(CH₂)_(y)—O—(CH₂)_(x)—CH═CH₂, —(CH₂)_(y)—O—(CH₂)_(x)—C(CH₃)═CH₂ or—(CH₂)_(y)—O—CH═CH₂, where x and y independently of one another are anumber from 1 to 21.

C₃-C₂₄Cycloalkenyl, e.g. C₅-C₁₂cycloalkenyl, C₃-C₁₂cycloalkenyl,C₃-C₈cycloalkenyl, stands both for individual alkyl ring systems andalso bridged alkyl ring systems and can be mono- or polyunsaturated,e.g. mono- or diunsaturated. Furthermore, the radicals can also containlinear or branched alkyl groups (as described above apart from thecorresponding number of carbon atoms). Examples are cyclopropenyl,cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclododecenyl,cycloicosenyl, in particular cyclopentenyl and cyclohexenyl, preferablycyclohexenyl.

C₇-C₂₄Arylalkyl is, for example, C₇-C₁₆arylalkyl, C₇-C₁larylalkyl. Thealkyl radical in this group can either be linear or branched. Examplesare benzyl, phenylethyl, α-methylbenzyl, phenylpentyl, phenylhexyl,α,α-dimethylbenzyl, naphthylmethyl, naphthylethyl, naphthyleth-1-yl ornaphthyl-1-methyl-eth-1-yl, in particular benzyl. SubstitutedC₇-C₂₄arylalkyl is substituted one to four times, e.g. once, twice orthree times, in particular once or twice, on the aryl ring.

C₈-C₂₄Arylcycloalkyl is e.g. C₉-C₁₆arylcycloalkyl, C₉-C₁₃arylcycloalkyland is cycloalkyl which is fused with one or more aryl rings. Examplesare

C₁-C₁₂Alkylthio stands for linear or branched radicals and is, forexample, C₁-C₈alkylthio, C₁-C₆alkylthio or C₁-C₄alkylthio. Examples aremethylthio, ethylthio, propylthio, isopropylthio, n-butylthio,sec-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio,heptylthio, 2,4,4-trimethylpentylthio, 2-ethylhexylthio, octylthio,nonylthio, decylthio or dodecylthio, in particular methylthio,ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio,isobutylthio, tert-butylthio, preferably methylthio.

C₁-C₈Alkylthio is likewise linear or branched and has, for example, themeanings given above apart from the corresponding number of carbonatoms.

C₁-C24Alkylene is linear or branched and is, for example,C₁-C₂₀alkylene, C₁-C₁₂alkylene, C₁-C₈alkylene, C₂-C₈alkylene,C₁-C₄alkylene, for example methylene, ethylene, propylene, isopropylene,n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene,hexylene, heptylene, octylene, nonylene, decylene, dodecylene,tetradecylene, heptadecylene, octadecylene, icosylene or e.g.C₁-C₁₂alkylene, for example ethylene, decylene,

C₂-C₁₈Alkylene is also linear or branched, e.g. C₂-C₈alkylene orC₂-C₄alkylene and has the meanings given above apart from thecorresponding number of carbon atoms.

If C₂-C₁₈alkylene is interrupted once or more than once by O, S or NR₁₄,then it is, for example, interrupted 1-9 times, e.g. 1-7 times or onceor twice by O, S or NR₁₄, and, for example, structural units such as—CH₂—O—CH₂—, —CH₂CH₂—O—CH₂CH₂—, —[CH₂CH₂O]_(z)—, where z=1 to 9,—(CH₂CH₂O)₇CH₂CH₂—, —CH₂—CH(CH₃)—O—CH₂—CH(CH₃)—, —CH₂—S—CH₂—,—CH₂CH₂—S—CH₂CH₂—, —CH₂CH₂CH₂—S—CH₂CH₂CH₂—, —(CH₂)₃—S—(CH₂)₃—S—(CH₂)₃—,—CH₂—(NR₁₄)—CH₂— or —CH₂CH₂—(NR₁₄)—CH₂CH₂— arise. The alkylene radicalscan be linear or branched and, if the alkylene radicals are interruptedby two or more O, S or NR₁₄ groups, then the O, S and NR₁₄ are notconsecutive, but in each case are separated from one another by at leastone methylene group.

C₂-C₂₄Alkenylene is mono- or polyunsaturated and linear or branched ande.g. C₂-C₁₈alkenylene or C₂-C₈alkenylene. Examples are ethenylene,propenylene, butenylene, pentenylene, hexenylene, octenylene, e.g.1-propenylene, 1-butenylene, 3-butenylene, 2-butenylene,1,3-pentadienylene, 5-hexenylene or 7-octenylene.

C₂-C₂₄Alkenylene, interrupted once or more than once by O, S, NR₁₄, ismono- or poly-unsaturated and linear or branched and is, for example,interrupted 1-9 times, e.g. 1-7 times or once or twice, by O, S or NR₁₄,where in the case of two or more O, S or NR₁₄, these are in each caseseparated from one another by at least one methylene group. Here, themeanings for C₂-C₂₄alkenylene are as defined above.

C₄-C₁₈Cycloalkylene is linear or branched and can be either anindividual ring or bridged alkyl rings, for example adamantyl. It ise.g. C₄-C₁₂cycloalkylene or C₄-C₈cycloalkylene, for examplecyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, inparticular cyclopentylene and cyclohexylene, preferably cyclohexylene.However, C₄-C₁₈cycloalkylene likewise stands for structural units suchas

in which r and s independently of one another are 0-12 and the sum r+sis ≦12, or

in which r and s independently of one another are 0-13 and the sum r+sis ≦13.

C₄-C₁₈Cycloalkylene interrupted once or more than once by O, S or NR₁₄stands for cycloalkylene units as described above which can beinterrupted either in the ring unit or in the side-chain unit e.g. 1-9times, 1-7 times or once or twice, by O, S or NR₁₄.

C₃-C₂₄Cycloalkenylene is linear or branched and can be either anindividual ring or bridged rings and is mono- or polyunsaturated. It ise.g. C₃-C₁₂cycloalkenylene or C₃-C₈cycloalkenylene, for examplecyclopentenylene, cyclohexenylene, cyclooctenylene, cyclododecenylene,in particular cyclopentenylene and cyclohexenylene, preferablycyclohexenylene. C₃-C₂₄Cycloalkenylene also, however, stands forstructural units such as

in which r and s independently of another are 0-12 and the sum r+s is≦12, or

in which r and s independently of one another are 0-13 and the sum r+sis ≦13.

C₅-C₁₈Cycloalkenylene has the meanings given above forC₃-C₂₄cycloalkenylene apart from the corresponding number of carbonatoms.

C₃-C₂₄Cycloalkenylene interrupted once or more than once by O, S or NR₁₄stands for cycloalkenylene units as described above which can beinterrupted either in the ring unit or in the side-chain unit e.g. 1-9times, 1-7 times or once or twice by O, S or NR₁₄. Examples are

Halogen is fluorine, chlorine, bromine or iodine, in particularfluorine, chlorine and bromine, preferably chlorine. R₁, R₁′, R₂, R₂′,R₃ and R₃′ as halogen are, in particular, chlorine.

If in each case two of the radicals R₁, R₂, R₃, R₄ or R₅ or in each casetwo of the radicals R₁₉, R₂₀, R₂₁, R₂₂ or R₂₃ form C₁-C₁₂alkylene, then,for example, the following structures

In connection with the present application, the term “and/or” means thatnot only one of the defined alternatives (substituents) may be present,but likewise two or more different defined alternatives (substituents)together, i.e. mixtures of different alternatives (substituents). Theterm “at least” is intended to define one or more than one, e.g. one ortwo or three, preferably one or two.

As O-, S- or N-containing 5- or 6-membered heterocyclic ring, Ar is e.g.furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. Said heterocyclicradicals can be mono- or polysubstituted, e.g. monosubstituted ordisubstituted, by halogen, linear or branched C₁-C₄alkyl, such asmethyl, ethyl, propyl, butyl, and/or C₁-C₄alkoxy. Examples thereof aredimethylpyridyl, dimethylpyrrolyl or methylfuryl.

Ar is, for example, 2-methylnaphth-2-yl, 2-methoxynaphth-2-yl,1,3-dimethyinaphth-2-yl, 2,8-dimethylnaphth-1-yl,1,3-dimethoxynaphth-2-yl, 1,3-dichloronaphth-2-yl,2,8-dimethoxynaphth-1-yl, 2,4,6-trimethylpyrid-3-yl,2,4-dimethoxyfuran-3-yl or 2,4,5-trimethylthien-3-yl.

Preference is given to compounds of the formula I in which Ar is aradical

Of particular interest are compounds of the formula I, in which R₁ andR₂ independently of one another are C₁-C₄alkyl, C₁-C₄alkoxy, C₁ or CF₃,in particular methyl or methoxy.

R₁ and R₂ are preferably identical.

R₁ and R₂ are preferably C₁-C₄alkyl or C₁-C₄alkoxy.

R₃, R₄ and R₅ in the compounds of the formula I are, in particular,independently of one another hydrogen, C₁-C₄alkyl, C₁ or C₁-C₄alkoxy, inparticular hydrogen, methyl or methoxy. R₃ is preferably C₁-C₄alkyl orC₁-C₄alkoxy, in particular methyl, methoxy or hydrogen, and R₄ and R₅are hydrogen.

R₆ in the compounds of the formula I is in particular C₁-C₂₄alkyl,unsubstituted or substituted by cycloalkenyl, CN, C(O)R₁₁, C(O)OR₁₁,C(O)N(R₁₄)₂, cycloalkyl, halogen; C₂-C₂₄alkyl which is interrupted onceor more than once by nonconsecutive O, S or NR₁₄ and which isunsubstituted or substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁,C(O)OR₁₁, phenyl and/or C(O)N(R₁₄)₂; C₂-C₂₄alkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); benzyl, cyclopentyl, cyclohexyl, C₄-C₂₄cycloalkyl which isuninterrupted or interrupted once or more than once by O, S and/or NR₁₄;or C₈-C₂₄arylcycloalkyl.

Compounds of the formula I in which R₁₂ and R₁₃ are e.g. hydrogen,C₁-C₄alkyl, phenyl or benzyl or C₂-C₁₂alkyl which is interrupted once ormore than once by nonconsecutive O atoms and which is unsubstituted oris substituted by OH and/or SH; or R₁₂ and R₁₃ together are piperidino,morpholino, or piperazino are likewise of interest. R₁₂ and R₁₃ arepreferably C₁-C₄alkyl, or R₁₂ and R₁₃ are together morpholino.

R₁₄ in the compounds of the formula I is, in particular, hydrogen,phenyl, C₁-C₄alkyl or C₂-C₄alkyl which is interrupted once or more thanonce by O or S and which is unsubstituted or substituted by OH and/orSH, preferably hydrogen and C₁-C₄alkyl.

M in the compounds of the formula I is preferably hydrogen or Li, inparticular Li.

Of particular interest are compounds of the formula I in which

R₁ and R₂ independently of one another are C₁-C₁₂alkyl, OR₁₁, CF₃ orhalogen;

R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl,OR₁, or halogen;

R₆ is C₁-C₁₂alkyl, unsubstituted or substituted by cycloalkenyl, CN,C(O)R₁₁, C(O)OR₁₁, phenyl, C(O)N(R₁₄)₂, cycloalkyl; C₂-C₁₂alkyl which isinterrupted once or more than once by nonconsecutive O, S or NR₁₄ andwhich is unsubstituted or substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN,C(O)R₁₁, C(O)OR₁₁ and/or C(O)N(R₁₄)₂; C₂-C₁₂alkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁, orN(R₁₂)(R₁₃); benzyl, cyclopentyl, cyclohexyl, C₄-C₁₂cycloalkyl which isuninterrupted or interrupted once or more than once by O, S and/or NR₁₄;or C₈-C₁₂arylcycloalkyl;

R₁₁ is H, C₁-C₁₂alkyl, cyclohexyl, cyclopentyl, phenyl or benzyl;

R₁₂ and R₁₃ independently of one another are C₁-C₁₂alkyl, cyclopentyl,cyclohexyl, phenyl, benzyl or C₂-C₁₂alkyl which is interrupted once ormore than once by nonconsecutive O atoms and which is unsubstituted orsubstituted by OH and/or SH; or R₁₂ and R₁₃ together are piperidino,morpholino or piperazino;

R₁₄ is hydrogen or C₁-C₁₂alkyl; and

M is hydrogen or Li.

Of specific interest are compounds of the formula I in which R₁ and R₂independently of one another are C₁-C₄alkyl or OR₁₁;

R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₄alkyl orOR₁₁;

R₆ is C₁-C₁₂alkyl, unsubstituted or substituted by CN, C(O)R₁₁,C(O)OR₁₁, C(O)N(R₁₄)₂;

C₂-C₁₂alkyl which is interrupted once or more than once bynonconsecutive O and which is unsubstituted or substituted by OR₁₁,SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, phenyl or C(O)N(R₁₄)₂;C₂-C₈alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O and which is unsubstituted or substituted byOR₁₁; benzyl, cyclopentyl, cyclohexyl, C₄-C₈cycloalkyl which isuninterrupted or interrupted by O, S or NR₁₄; or C₈-C₁₂arylcycloalkyl;

R₁₁ is H or C₁-C₁₂alkyl;

R₁₄ is hydrogen or C₁-C₈alkyl; and

M is Li.

Examples of compounds of the formula I are

lithium (2,6-dimethylbenzoyl)ethylphosphine, lithium(2,6-diethylbenzoyl)ethylphosphine, lithium(2,4,6-trimethylbenzoyl)ethylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)ethylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)ethylphosphine, lithium(2,4,6-triisopropylbenzoyl)ethylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)ethylphosphine, lithium(2,4,6-tri-tert-butylbenzoyl)ethylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphine, lithium(2,6-diphenoxymethylbenzoyl)ethylphosphine, lithium(2,3,6-trimethylbenzoyl)ethylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)ethylphosphine, lithium(2-phenyl-6-methylbenzoyl)ethylphosphine, lithium(2,4,6-trimethoxybenzoyl)ethylphosphine, lithium(2,4-dimethoxybenzoyl)ethylphosphine, lithium(2,3,6-trimethoxybenzoyl)ethylphosphine, lithium(2,6-diethoxybenzoyl)ethylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)ethylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)ethylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)ethylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)ethylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)ethylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)ethylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)ethylphosphine, lithium(2,6-dichlorobenzoyl)ethylphosphine, lithium(2,4,6-trichlorobenzoyl)ethylphosphine, lithium(2,3,6-trichlorobenzoyl)ethylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)ethy 1-phosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)ethylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)ethylphosphine, lithium(2-chloro-6-methylbenzoyl)ethylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)ethylphosphine, lithium(2-methoxy-6-chlorobenzoyl)ethylphosphine, lithium(2,6-bis(trifluoromethyl)benzoyl)ethylphosphine, lithium(2-chloro-6-methylthiobenzoyl)ethylphosphine, lithium(2,6-dibromobenzoyl)ethylphosphine, lithium(2,6-dimethylbenzoyl)-n-butylphosphine, lithium(2,6-diethylbenzoyl)-n-butylphosphine, lithium(2,4,6-trimethylbenzoyl)-n-butylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)-n-butylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)-n-butylphosphine, lithium(2,4,6-triisopropylbenzoyl)-n-butylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)-n-butylphosphine, lithium(2,4,6-tri-tertbutylbenzoyl)-n-butylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphine, lithium(2,6-diphenoxymethylbenzoyl)-n-butylphosphine, lithium(2,3,6-trimethylbenzoyl)-n-butylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)-n-butylphosphine, lithium(2-phenyl-6-methylbenzoyl)-n-butylphosphine, lithium(2,4,6-trimethoxybenzoyl)-n-butylphosphine, lithium(2,4-dimethoxybenzoyl)-n-butylphosphine, lithium(2,3,6-trimethoxybenzoyl)-n-butylphosphine, lithium(2,6-diethoxybenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)-n-butylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)-n-butylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)-n-butylphosphine, lithium(2,6-dichlorobenzoyl)-n-butylphosphine, lithium(2,4,6-trichlorobenzoyl)-n-butylphosphine, lithium(2,3,6-trichlorobenzoyl)-n-butylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)-n-butylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)-n-butylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)-n-butylphosphine, lithium(2-chloro-6-methylbenzoyl)-n-butylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)-n-butylphosphine, lithium(2-methoxy-6-chlorobenzoyl)-n-butylphosphine, lithium(2,6-bis(trifluoromethyl)benzoyl)-n-butylphosphine, lithium(2-chloro-6-methylthiobenzoyl)-n-butylphosphine, lithium(2,6-dibromobenzoyl)-n-butylphosphine, lithium(2,6-dimethylbenzoyl)isobutylphosphine, lithium(2,6-diethylbenzoyl)isobutylphosphine, lithium(2,4,6-trimethylbenzoyl)isobutylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)isobutylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)isobutylphosphine, lithium(2,4,6-triisopropylbenzoyl)isobutylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)isobutylphosphine, lithium(2,4,6-tri-tertbutylbenzoyl)isobutylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphine, lithium(2,6-diphenoxymethylbenzoyl)isobutylphosphine, lithium(2,3,6-trimethylbenzoyl)isobutylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)isobutylphosphine, lithium(2-phenyl-6-methylbenzoyl)isobutylphosphine, lithium(2,4,6-trimethoxybenzoyl)isobutylphosphine, lithium(2,4-dimethoxybenzoyl)isobutylphosphine, lithium(2,3,6-trimethoxybenzoyl)isobutylphosphine, lithium(2,6-diethoxybenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)isobutylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)isobutylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)isobutylphosphine, lithium(2,6-dichlorobenzoyl)isobutylphosphine, lithium(2,4,6-trichlorobenzoyl)isobutylphosphine, lithium(2,3,6-trichlorobenzoyl)isobutylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)isobutylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)isobutylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)isobutylphosphine, lithium(2-chloro-6-methylbenzoyl)isobutylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)isobutylphosphine, lithium(2-methoxy-6-chlorobenzoyl)isobutylphosphine, lithium(2,6-bis(trifluoromethyl)-benzoyl)isobutylphosphine, lithium(2-chloro-6-methylthiobenzoyl)isobutylphosphine, lithium(2,6-dibromobenzoyl)isobutylphosphine, lithium(2,6-dimethylbenzoyl)-o-methylpropylphosphine, lithium(2,6-diethylbenzoyl)-1-methylpropylphosphine, lithium(2,4,6-trimethylbenzoyl)-1-methylpropylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)-1-methylpropylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)-1-methylpropylphosphine, lithium(2,4,6-triisopropylbenzoyl)-1-methylpropylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)-1-methylpropylphosphine, lithium(2,4,6-tri-tert-butylbenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)-1-methylpropylphosphine, lithium(2,6-diphenoxymethylbenzoyl)-1-methylpropylphosphine, lithium(2,3,6-trimethylbenzoyl)-1-methylpropylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)-1-methylpropylphosphine, lithium(2-phenyl-6-methylbenzoyl)-1-methylpropylphosphine, lithium(2,4,6-trimethoxybenzoyl)-1-methylpropylphosphine, lithium(2,4-dimethoxybenzoyl)-1-methylpropylphosphine, lithium(2,3,6-trimethoxybenzoyl)-1-methylpropylphosphine, lithium(2,6-diethoxybenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)-1-methylpropylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)-1-methylpropylphosphine, lithium(2,6-dichlorobenzoyl)-1-methylpropylphosphine, lithium(2,4,6-trichlorobenzoyl)-1-methylpropylphosphine, lithium(2,3,6-trichlorobenzoyl)-1-methylpropylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)-1-methylpropylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)-1-methylpropylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)-1-methylpropylphosphine, lithium(2-chloro-6-methylbenzoyl)-1-methylpropylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)-1-methylpropylphosphine, lithium(2-methoxy-6-chlorobenzoyl)-1-methylpropylphosphine, lithium(2,6-bis-(trifluoromethyl)benzoyl)-1-methylpropylphosphine, lithium(2-chloro-6-methylthiobenzoyl)-1-methylpropylphosphine, lithium(2,6-dibromobenzoyl)-1-methylpropylphosphine, lithium(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-diethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,6-triisopropylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,6-tri-tert-butylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-dimethyl-4-tertbutylbenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-diphenoxymethylbenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,3,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2-phenyl-6-methylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,6-trimethoxybenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,6-trimethoxybenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-diethoxybenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-dimethoxy-4-methylbenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-dimethoxy-3-bromobenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-dimethoxy-3-chlorobenzoyl)-2,4,4-trimethylpentylphosphine,lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)-2,4,4-trimethylpentylphosphine,lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine,lithium(2,3,6-trimethoxy-5-bromobenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,4,6-trichlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,6-trichlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2-chloro-6-methylbenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2-methoxy-6-chlorobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-bis(trifluoromethyl)benzoyl)-2,4,4-trimethylpentylphosphine,lithium (2-chloro-6-methylthiobenzoyl)-2,4,4-trimethylpentylphosphine,lithium (2,6-dibromobenzoyl)-2,4,4-trimethylpentylphosphine, lithium(2,6-dimethylbenzoyl)cyclopentylphosphine, lithium(2,6-diethylbenzoyl)cyclopentylphosphine, lithium(2,4,6-trimethylbenzoyl)cyclopentylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)cyclopentylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)cyclopentylphosphine, lithium(2,4,6-trisopropylbenzoyl)cyclopentylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)cyclopentylphosphine, lithium(2,4,6-tri-tert-butylbenzoyl)cyclopentylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphine, lithium(2,6-diphenoxymethylbenzoyl)cyclopentylphosphine, lithium(2,3,6-trimethylbenzoyl)cyclopentylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)cyclopentylphosphine, lithium(2-phenyl-6-methylbenzoyl)cyclopentylphosphine, lithium(2,4,6-trimethoxybenzoyl)cyclopentylphosphine, lithium(2,4-dimethoxybenzoyl)cyclopentylphosphine, lithium(2,3,6-trimethoxybenzoyl)cyclopentylphosphine, lithium(2,6-diethoxybenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)cyclopentylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)cyclopentylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)cyclopentylphosphine, lithium(2,6-dichlorobenzoyl)cyclopentylphosphine, lithium(2,4,6-trichlorobenzoyl)cyclopentylphosphine, lithium(2,3,6-trichlorobenzoyl)cyclopentylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)cyclopentylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)cyclopentylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)cyclopentylphosphine, lithium(2-chloro-6-methylbenzoyl)cyclopentylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)cyclopentylphosphine, lithium(2-methoxy-6-chlorobenzoyl)-cyclopentylphosphine, lithium(2,6-bis(trifluoromethyl)benzoyl)cyclopentylphosphine, lithium(2-chloro-6-methylthiobenzoyl)cyclopentylphosphine, lithium(2,6-dibromobenzoyl)cyclopentylphosphine, lithium(2,6-dimethylbenzoyl)cyclohexylphosphine, lithium(2,6-diethylbenzoyl)cyclohexylphosphine, lithium(2,4,6-trimethylbenzoyl)cyclohexylphosphine, lithium(2,3,4,5,6-pentamethylbenzoyl)cyclohexylphosphine, lithium(2,3,5,6-tetramethylbenzoyl)cyclohexylphosphine, lithium(2,4,6-triisopropylbenzoyl)cyclohexylphosphine, lithium(2,4,5,6-tetramethylbenzoyl)cyclohexylphosphine, lithium(2,4,6-tri-tert-butylbenzoyl)cyclohexylphosphine, lithium(2,6-dimethyl-4-tert-butylbenzoyl)cyclohexylphosphine, lithium(2,6-diphenoxymethylbenzoyl)cyclohexylphosphine, lithium(2,3,6-trimethylbenzoyl)cyclohexylphosphine, lithium(2,3,4,6-tetramethylbenzoyl)cyclohexylphosphine, lithium(2-phenyl-6-methylbenzoyl)cyclohexylphosphine, lithium(2,4,6-trimethoxybenzoyl)cyclohexylphosphine, lithium(2,4-dimethoxybenzoyl)cyclohexylphosphine, lithium(2,3,6-trimethoxybenzoyl)cyclohexylphosphine, lithium(2,6-diethoxybenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-3,5-dimethylbenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-4-methylbenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-3-bromobenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-3-chlorobenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-3-chloro-5-bromobenzoyl)cyclohexylphosphine, lithium(2,6-dimethoxy-3,5-dichlorobenzoyl)cyclohexylphosphine, lithium(2,3,6-trimethoxy-5-bromobenzoyl)cyclohexylphosphine, lithium(2,6-dichlorobenzoyl)cyclohexylphosphine, lithium(2,4,6-trichlorobenzoyl)cyclohexylphosphine, lithium(2,3,6-trichlorobenzoyl)cyclohexylphosphine, lithium(2,3,5,6-tetrachlorobenzoyl)cyclohexylphosphine, lithium(2,3,4,5,6-pentachlorobenzoyl)cyclohexylphosphine, lithium(2,6-dichloro-3-methylbenzoyl)cyclohexylphosphine, lithium(2-chloro-6-methylbenzoyl)cyclohexylphosphine, lithium(2-methoxy-3,6-dichlorobenzoyl)cyclohexylphosphine, lithium(2-methoxy-6-chlorobenzoyl)cyclohexylphosphine, lithium(2,6-bis(trifluoromethyl)benzoyl)cyclohexylphosphine, lithium(2-chloro-6-methylthiobenzoyl)cyclohexylphosphine, lithium(2,6-dibromobenzoyl)cyclohexylphosphine.

The compounds of the formula (I′) are, for example, selectively obtainedby reaction of acyl halides (IV) with dimetalated organophosphines (V):

Ar and R₆ have the meanings described above. X is Cl or Br and M₁ is Na,Li or K.

The starting materials are advantageously reacted in the molar ratio1:1. A slight excess of one or other of the components, e.g. up to 20%,is not, however, critical. In this case too the desired product isformed, although the proportion of undesired byproduct may beinfluenced.

The reaction is advantageously carried out in a solvent. In particular,as solvents, it is possible to use ethers which are liquid atatmospheric pressure and room temperature. Examples are dimethyl ether,diethyl ether, methyl propyl ether, 1,2-dimethoxyethane,bis-(2-methoxyethyl) ether, dioxane or tetrahydrofuran. Preference isgiven to using tetrahydrofuran.

The reaction temperatures are advantageously −60° C. to +120° C., e.g.−40° C. to 100° C., for example −20° C. to +80° C.

It is advisable to stir the reaction mixture.

It is advantageous to initially introduce the compound of the formula Vand to add dropwise the compound of the formula IV at the temperaturesgiven above. Here, the compound of the formula IV can be added without adiluent or else diluted with the reaction solvent. If desired, thecourse of the reaction can be monitored using methods customary in theart, for example NMR, for example ³¹P-NMR, chromatography (thin-layer,HPLC, GC) etc.

In the reactions described above, it is essential to work in an inertgas atmosphere, e.g. with a protective gas such as argon or nitrogen, inorder to exclude atmospheric oxygen.

In order to prepare compounds of the formula I in which M is hydrogen,the reaction given above is followed by a hydrolysis step:

The procedure for such hydrolysis reactions is known to the personskilled in the art and is carried out under generally customaryconditions. The hydrolysis of metalated primary and secondary phosphinesis described, for example, in Houben-Weyl, XII/1, pages 56-57. Likewiseconceivable is the preparation of compounds of the formula (I) whereM=hydrogen, by reaction between a compound of the formula (IV) and analkylphosphine compound in the presence of an acid-binding agent, suchas barium carbonate, calcium carbonate or potassium carbonate, asdescribed, for example, in Houben-Weyl, XII/1, pages 73-74 or in K.Issleib and R. Kümmel, Z. Naturf. B (1967), 22, 784.

The compounds of the formula I according to the invention are identifiedby ³¹P-NMR spectroscopy and are stable in the solution under inert gasat room temperature for a number of weeks.

The invention also provides a process for the selective preparation ofcompounds of the formula I by

(1) reaction of an acyl halide of the formula IV

in which

Ar is as defined above, and

X is Cl or Br;

with a dimetalated organophosphine of the formula V

in which

R₆ is as defined above; and

M₁ is Na, Li or K;

in the molar ratio 1:1; and

(2) where appropriate, subsequent hydrolysis if compounds of the formulaI in which M is hydrogen are to be obtained.

The acyl halides (IV) used as starting material are known substances,some of which are available commercially, or can be prepared analogouslyto known compounds.

A method for the preparation of metalated alkylphosphines is, forexample, the reaction of suitable alkylphosphines with the correspondingalkali metal, alkali metal hydride or an alkyllithium compound.

(M₁ is as defined above)

The reaction is advantageously carried out with the exclusion of air inan inert solvent at temperatures of, for example, −80° C. to +120° C.Advantageously, 2 to 4 mole equivalents of the alkali metals, alkalimetal hydrides or alkyllithium compound are used. Suitable solvents aree.g. ethers, as described above, or inert solvents, such as alkanes,cycloalkanes, aromatic solvents such as toluene, xylene, mesitylene.

The preparation of the alkylphosphines R₆-PH₂ is generally known. Forexample, the compounds can, for example, be obtained by reacting PH₃with alkenes in the presence of a free-radical former or by reducingalkylphosphine chlorides e.g. with lithium aluminium hydride. These andother methods are, for example, described in “Organic PhosphorousCompounds, Vol. 1-7, Wiley-Interscience 1972, Editors R. M. Kosalapoffand L. Maier”.

The compounds of the formula I are particularly suitable for thepreparation of unsymmetrical mono- and bisacylphosphines, mono- andbisacylphosphine oxides, and mono- and bisacylphosphine sulfides.“Unsymmetrical” means in this connection that in the bisacylphosphines,bisacylphosphine oxides and sulfides, two different acyl groups arepresent, and in the monoacylphosphines, monoacylphosphine oxides andsulfides, in addition to the acyl group, two different radicals arebonded to the phosphorus atom.

Such “unsymmetrical” mono- and bisacylphosphines, mono- andbisacylphosphine oxides, and mono- and bisacylphosphine sulfides are,with a few exceptions, novel.

Accordingly, the invention also provides compounds of the formula II

wherein

A is O or S;

x is 0 or 1;

Ar is a group

or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy;

R₁ and R₂ independently of one another are C₁-C₂₀alkyl, OR₁₁, CF₃ orhalogen;

R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₂₀alkyl,OR₁₁ or halogen;

or in each case two of the radicals R₁, R₂, R₃, R₄ and R₅ together formC₁-C₂₀alkylene which can be interrupted by O, S or NR₁₄;

R₆ is C₁-C₂₄alkyl, unsubstituted or substituted by C₅-C₂₄cycloalkenyl,phenyl, CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁,N(R₁₄)C(O)N(R₁₄), OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁,SR₁₁, N(R₁₂)(R₁₃) or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₅-C₂₄cycloalkenyl which is uninterrupted or interrupted once or morethan once by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₇-C₂₄arylalkyl which is unsubstituted or substituted on the aryl groupby C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen;

C₄-C₂₄cycloalkyl which is uninterrupted or interrupted once or more thanonce by O, S and/or NR₁₄ and which is unsubstituted or substituted byOR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

or C₈-C₂₄arylcycloalkyl or C8-C₂₄arylcycloalkenyl;

R₁₁ is H, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl orC₂-C₂₀alkyl which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted by OHand/or SH;

R₁₂ and R₁₃ independently of one another are hydrogen, C₁-C₂₀alkyl,C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl which is interrupted onceor more than once by O or S and which is unsubstituted or substituted byOH and/or SH; or R₁₂ and R₁₃ together are C₃-C₅alkylene which isuninterrupted or interrupted by O, S or NR₁₄;

Y₁ is C₁-C₁₈alkyl which is unsubstituted or substituted by one or morephenyl; C₁-C₁₈-halogenoalkyl; C₂-C₁₈alkyl which is interrupted once ormore than once by O or S and which can be substituted by OH and/or SH;unsubstituted C₃-C₁₈cycloalkyl or C₃-C₁₈cycloalkyl substituted byC₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; C₂-C₁₈alkenyl; or Y₁ is OR₁₁,N(R₁₂)(R₁₃) or one of the radicals

or Y₁ is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy;

Y₂ is a direct bond; unsubstituted or phenyl-substituted C₁-C₁₈alkylene;unsubstituted C₄-C₁₈-cycloalkylene or C₄-C₁₈cycloalkylene substituted byC₁-C₁₂alkyl, OR₁₁, halogen and/or phenyl; unsubstitutedC₅-C₁₈cycloalkenylene or C₅-C₁₈cycloalkenylene substituted byC₁-C₁₂alkyl, OR₁₁, halogen and/or phenyl; unsubstituted phenylene orphenylene substituted one to four times by C₁-C₁₂alkyl, OR₁₁, halogen,—(CO)OR₁₄, —(CO)N(R₁₂)(R₁₃) and/or phenyl;

or Y₂ is a radical

where these radicals are unsubstituted or are substituted one to fourtimes on one or both aromatic ring(s) by C₁-C₁₂alkyl, OR₁₁, halogenand/or phenyl;

Y₃ is O, S, SO, SO₂, CH₂, C(CH₃)₂, CHCH₃, C(CF₃)₂, (CO), or a directbond;

R₁₄ is hydrogen, phenyl, C₁-C₁₂alkyl or C₂-C₁₂alkyl which is interruptedonce or more than once by O or S and which can be substituted by OHand/or SH;

R₁′ and R₂′ independently of one another have the same meanings as givenfor R₁ and R₂; and

R₃′, R₄′ and R₅′ independently of one another have the same meanings asgiven for R₃, R₄ and R₅; or in each case two of the radicals R₁′, R₂′,R₃′, R₄′ and R₅′ together form C₁-C₂₀alkylene which may be interruptedby O, S or —NR₁₄;

with the proviso that Y₁ is not identical to Ar.

In the compounds of the formula II, the preferred meanings of theradicals R₁, R₂, R₃, R₄, R₅ and R₆ are analogous to those given abovefor the compounds of the formula I.

In the compounds of the formula II, x is preferably 1. In particular, Ais oxygen and Ar is a group

Of particular importance are compounds of the formula II in which Y₁ isC₁-C₁₂alkyl, in particular branched C₁-C₁₂alkyl; unsubstitutedC₃-C₁₈cycloalkyl or C₃-C₁₈cycloalkyl substituted by C₁-C₂₀alkyl, OR₁₁,CF₃ or halogen; or is

Y₁ as C₁-C₁₂alkyl is preferably branched in the a-position relative tothe bond to the CO group. The carbon atom in the α-position relative tothe CO group is preferably a tertiary carbon atom.

The preferred meanings for R₁′, R₂′, R₃′, R₄′ and R₅′ are analogous tothose preferred meanings of R₁, R₂, R₃, R₄ and R₅ given above forformula I.

Also of interest are compounds of the formula II in which R₁, R₂ and R₃are C₁-C₄alkyl, in particular methyl; R₁′ and R₂′ are C₁-C₄alkoxy, inparticular methoxy, or chlorine; and R₄, R₅, R₃′, R₄′ and R₅′ arehydrogen.

In preferred compounds of the formula II,

A is oxygen and x is 1;

R₁ and R₂ are C₁-C₄alkyl, C₁-C₄alkoxy, Cl or CF₃;

R₃ is hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy;

R₄ and R₅ are hydrogen;

R₆ is C₁-C₁₂alkyl, unsubstituted or substituted by cycloalkenyl, CN,C(O)R₁₁, C(O)OR₁₁, phenyl, C(O)N(R₁₄)₂, cycloalkyl; C₂-C₁₂alkyl which isinterrupted once or more than once by nonconsecutive O, S or NR₁₄ andwhich is unsubstituted or substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN,C(O)R₁₁, C(O)OR₁₁ and/or C(O)N(R₁₄)₂; C₂-C₁₂alkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); benzyl, cyclopentyl, cyclohexyl, C₄-C₁₂cycloalkyl which isuninterrupted or interrupted once or more than once by O, S and/or NR₁₄;or C₈-C₁₂arylcycloalkyl;

R₁₁ is H, C₁-C₁₂alkyl, cyclohexyl, cyclopentyl, phenyl or benzyl;

R₁₂ and R₁₃ independently of one another are C₁-C₁₂alkyl, cyclopentyl,cyclohexyl, phenyl, benzyl or C₂-C₁₂alkyl which is interrupted once ormore than once by nonconsecutive O atoms and which is unsubstituted orsubstituted by OH and/or SH; or R₁₂ and R₁₃ together are piperidino,morpholino or piperazino;

R₁₄ is hydrogen or C₁-C₁₂alkyl; and

Y₁ is C₁-C₁₂alkyl or

R₁′ and R₂′ have the same meanings as given for R₁ and R₂; and

R₃′, R₄′ and R₅′ independently of one another have the same meanings asgiven for R₃, R₄ and R₅.

Examples of preferred compounds of the formula II are

(2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)ethylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)ethylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)ethylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)ethylphosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}ethylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)ethylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)ethylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)ethylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}ethylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)ethylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)ethylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)ethylphosphine oxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)ethylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)ethylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)ethylphosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifIuoromethyl)benzoyl}ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)ethylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}ethylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)-n-butylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)-n-butylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-n-butylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)-n-butylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)-n-butylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-n-butylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)-n-butylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-n-butylphosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-n-butylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)-n-butylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)-n-butylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)-n-butylphosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis-(trifluoromethyl)benzoyl}-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)-n-butylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)-n-butylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)-n-butylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-n-butylphosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-n-butylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)-n-butylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)-n-butylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-n-butylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-n-butylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)-n-butylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)-n-butylphosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)-n-butylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-n-butylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)isobutylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)isobutylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)isobutylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)isobutylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)isobutylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)isobutylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)isobutylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)isobutylphosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)isobutylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)isobutylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)isobutylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)isobutylphosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}isobutylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)isobutylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)isobutylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)isobutylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)isobutylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)isobutylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)isobutylphosineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)isobutylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis-(trifluoromethyl)benzoyl}isobutylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(b-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)-(1-methylpropyl)-phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)-(1-methylpropyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)-(2,4,4-trimethylpentyl)phosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-(2,4,4-trimethylpentyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)cyclopentylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}-cyclopentylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)cyclopentylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)cyclopentylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)cyclopentylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclopentylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclopentylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclopentylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)cyclopentylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclopentylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)cyclopentylphosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)cyclopentylphosphineoxide, (2,6-dimethy-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)cyclopentylphosphine oxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclopentylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-bis(trifluoromethyl)benzoylcyclopentylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dimethylbenzoyl)cyclohexylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethylbenzoyl)cyclohexylphosphine(2,4,6-trimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4-dimethoxybenzoyl)cyclohexylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-diethoxybenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclohexylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,6-dichlorobenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethylbenzoyl)-{2,6-bimethyl-benzoyl}cyclohexylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dimethylbenzoyl)cyclohexylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethy-4-tert-butylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trimethoxybenzoyl)cyclohexylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4-dimethoxybenzoyl)cyclohexylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-diethoxybenzoyl)cxcyclohexphosphineoxide,(2,6-dimethoxybenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclohexylphosphineoxide, (2,6-dimethoxybenzoyl)-(2,6-dichlorobenzoyl)cyclohexylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,6-trichlorobenzoyl)cyclohexylphosphineoxide,(2,6-dimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethylbenzoyl)cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trimethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4-dimethoxybenzoyl)cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-diethoxybenzoyl)cyclohexylphosphineoxide,(2,6-dimethylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,6-dichlorobenzoyl)cyclohexylphosphineoxide, (2,6-dimethylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclohexylphosphineoxide,(2,6-dimethylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethylbenzoyl)cyclohexylphosphineoxide, (2,4,6-trimethoxybenzoyl)-(2,6-diethylbenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4,6-trimethylbenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,4-dimethoxybenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-diethoxybenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-(2,6-dichlorobenzoyl)cyclohexylphosphineoxide,(2,4,6-trimethoxybenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethyl-4-tert-butylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trimethoxybenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4-dimethoxybenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-diethoxybenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dimethoxy-4-methylbenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,6-dichlorobenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-(2,4,6-trichlorobenzoyl)cyclohexylphosphineoxide,(2,6-dimethyl-4-tert-butylbenzoyl)-{2,6-bis(trifluoromethyl)benzoyl}cyclohexylphosphineoxide.

The compounds of the formula II where x=0 (formula II′) are obtained byreacting an alkylacylphosphine of the formula I with an acid halide ofthe formula (IV):

The meanings of the radicals Ar, R₆, M, X and Y, are as described above.The starting materials are advantageously reacted in a molar ratio of1:1. A slight excess of one or other of the components, e.g. up to 20%,is, however, not critical. The desired product forms in this case too,although the proportion of undesired byproduct can be influenced. Thereaction conditions for this reaction correspond to those given above inconnection with the preparation of the compounds of the formula I.

Compounds of the formula II where x=1 and A is oxygen are prepared byoxidation of the compounds of the formula (II′), and compounds of theformula II where A is sulfur are prepared by sulfurization of thecompounds of the formula II′:

Prior to the oxidation or sulfurization, the phosphine II′ can beisolated by customary separation methods familiar to the person skilledin the art, although the reaction can also be carried out immediatelyafter the previous reaction step without isolation of the phosphine.

During the preparation of the oxide, the oxidation of the phosphine iscarried out using oxidizing agents customary in the art. Suitableoxidizing agents are primarily hydrogen peroxide and organic peroxycompounds, for example peracetic acid or t-butyl hydroperoxide, air orpure oxygen.

The oxidation is advantageously carried out in solution. Suitablesolvents are aromatic hydrocarbons, for example benzene, toluene,m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatichydrocarbons, e.g. alkanes and alkane mixtures, such as petroleum ether,hexane or cyclohexane. Further suitable examples are dimethyl ether,diethyl ether, methyl propyl ether, 1,2-dimethoxyethane,bis(2-methoxyethyl) ether, dioxane or tetrahydrofuran. Preference isgiven to using toluene.

The reaction temperature during the oxidation is advantageously keptbetween 0° and 120° C., preferably between 20° and 80° C.

The reaction products of the formula (II) can be isolated and purifiedby customary processing measures familiar to the person skilled in theart.

The preparation of the respective sulfide is carried out by reactionwith sulfur. The bisacylphosphines (II′) are here reacted with anequimolar to 2-fold molar amount of elemental sulfur e.g. without adiluent or optionally in a suitable inert organic solvent. Examples ofsuitable solvents are those described for the oxidation reaction. It is,however, also possible to use, for example, aliphatic or aromaticethers, for example dibutyl ether, dioxane, diethylene glycol dimethylether or diphenyl ether at temperatures of from 20° to 250° C.,preferably 60° to 120° C. The resulting bisacylphosphine sulfide, or itssolution is advantageously freed from any elemental sulfur which maystill be present by filtration. Following removal of the solvent, thebisacylphosphine sulfide can be isolated in pure form by distillation,recrystallization or chromatographic separation methods.

It is advantageous to carry out all of the reactions described abovewith the exclusion of air in an inert gas atmosphere, e.g. undernitrogen or argon gas. Moreover, stirring of the respective reactionmixture is advantageously appropriate.

The invention likewise provides a process for the preparation of thecompounds of the formula II, from compounds of the formula I as startingmaterials, by

(1) reaction of an acyl halide of the formula IV

in which

Ar is as defined above, and

X is Cl or Br;

with a dimetalated organophosphine of the formula V

in which

R₆ is as defined above; and

M₁ is Na, Li or K;

in the molar ratio of approximately 1:1;

(2) subsequent reaction of the product with an acyl halide of theformula IVa

in which

Y₁ is as defined above; and

X is as defined above;

with the proviso that the acyl halide of the formula IV is not identicalto the acyl halide of the formula IVa;

in the molar ratio of approximately 1:1; and,

(3) if compounds of the formula II in which A is oxygen or sulfur are tobe obtained, subsequent oxidation or sulfurization of the resultingphosphine compounds.

Furthermore, the compounds of the formula II can also be prepared byreacting the compound of the formula I with phosgene, analogously to thedescription in “W. A. Henderson et al., J. Am. Chem. Soc. 1960, 82,5794” or “GB 904 086” or in “Organic Phosphorous Compounds, Editors: R.M. Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.1, page 28” or“Houben-Weyl, Methoden der Organischen Chemie, Vol. XII/1, page 201”, togive the corresponding phosphine chloride (Ii). Compounds of the formula(Ii) can, as described in “Organic Phosphorous Compounds, Editors: R. M.Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.4, pages 268-269”,be reacted with alcohols to give compounds of the formula (Iii), whichare then reacted directly with an acyl halide of the formula IVa, inanalogy with the description in U.S. Pat. No. 4,324,744 (byMichaelis-Arbuzov reaction), to give compounds of the formula II. Inthis case, the oxidation step is superfluous.

Ar and Y₁ are as defined in claim 1, although Ar and Y₁ in this case mayalso be the same radical; X is Cl or Br; M and R₆ are likewise asdefined in claim 1, and R is any alcohol radical, e.g. C₁-C₁₂alkyl,C₅-C₈cycloalkyl, for example cyclopentyl or cyclohexyl, or benzyl.

The chlorination with phosgene with the elimination of carbon monoxideis advantageously carried out by introducing phosgene, with stirring,into a solution of (I) in an inert solvent. For example, phosgene isintroduced at −70° C. to 20° C., in particular at −40°C. to 0° C.Solvents which may be used are, for example, chlorinated alkanes, forexample dichloromethane, dichloroethane or tetrachloromethane; alkanes,for example hexane; cycloalkanes, for example cyclohexane, or aromaticsolvents, for example toluene. The isolation of (Ii) is carried out, forexample, by distillation under reduced pressure.

Such reactions are also described e.g. by R. Schmutzler et al. in, Z.Anorg. Allg. Chemie 1999, 625, pages 1979-1984.

The conversion of (Ii) to (Iii) is carried out for example in an inertsolvent in the presence of a tertiary amine, for example triethylamine,tributylamine or pyridine. Here, the alcohol (ROH) is advantageouslyadded dropwise to a solution (Ii) and tertiary amine in the solvent. Theaddition is preferably carried out at a temperature of from 60° C. to140° C. Solvents which may be used are, for example, chlorinatedalkanes, such as tetrachloromethane, dichloromethane, dichloroethane;alkanes, for example hexane; cycloalkanes, for example cyclohexane; oraromatic solvents, for example toluene. The isolation of (Iii) iscarried out, for example, by distillation under reduced pressure. Suchreactions have also been published e.g. by Y. A. Veits et al., in J.Gen. Chem. (USSR) 1991, 61, pages 108 ff.

The conversion of compounds of the formula (Iii) to compounds of theformula (II) is carried out by adding corresponding acyl halides (IVa)to a solution of (Iii) in an inert solvent. Here, the acyl halide isadvantageously dissolved in the same solvent in which the previousreaction step has taken place. The addition is carried out, for example,at a temperature of from 40° C. to 140° C., preferably at 60° C. to 120°C., the alkyl halide (RCI) liberated during the reaction advantageouslybeing removed by distillation from the reaction solution. Solvents whichmay be used here are, for example, alkanes, for example hexane, octane;cycloalkanes, for example cyclohexane; ethers, for example tert-butylmethyl ether, tetrahydrofuran, dioxane; or aromatic solvents, forexample toluene or xylene. The compounds of the structure (II) areadvantageously isolated and purified, for example, by distillation underreduced pressure, crystallization or by chromatography.

Compounds of the formula (Iii) can be oxidized using suitable oxidizingagents, such as peroxo acids, hydrogen peroxide or hydrogenperoxide/urea, to give the corresponding phosphinic esters (Iiii):

This preparation process is novel. The compounds prepared in this wayare also photoinitiators and are, for example, as those described inU.S. Pat. No. 4,324,744.

The invention thus also provides a process for the preparation ofcompounds of the formula II in which A is oxygen and x is 1, by

(1) reaction of the compounds of the formula (I), as described above,

in which

Ar, M and R₆ are as described above,

with phosgene to give the corresponding phosphine chloride (Ii)

(2) subsequent reaction with an alcohol to give the compound of theformula (Iii)

in which

R is the radical of an alcohol, in particular C₁-C₁₂alkyl,C₅-C₈cycloalkyl or benzyl; and

(3) reaction of the resulting compound of the formula (Iii) with an acylhalide

in which

Y₁ is as defined above, and

X is Cl or Br, to give a compound of the formula II in which Y₁ and Ardo not necessarily have to be different.

As already mentioned, slightly unsymmetrical monoacylphosphines,monoacylphosphine oxides or sulfides can also be obtained from thecompounds of the formula I.

The invention thus also provides compounds of the formula III

in which

A is O or S;

x is 0 or 1;

Ar is a group

or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy;

R₁ and R₂ independently of one another are C₁-C₂alkyl, OR₁₁, CF₃ orhalogen;

R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₂₀alkyl,OR₁₁ or halogen;

or in each case two of the radicals R₁, R₂, R₃, R₄ and R₅ together formC₁-C₂₀alkylene which can be interrupted by O, S or -NR₁₄;

R₆ is C₁-C₂₄alkyl, unsubstituted or substituted by C₅-C₂₄cycloalkenyl,phenyl, CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁,N(R₁₄)C(O)N(R₁₄), OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁,SR₁₁, N(R₁₂)(R₁₃) or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₅-C₂₄cycloalkenyl which is uninterrupted or interrupted once or morethan once by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

C₇-C₂₄arylalkyl which is unsubstituted or substituted on the aryl groupby C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen;

C₄-C₂₄cycloalkyl which is uninterrupted or interrupted once or more thanonce by O, S and/or NR₁₄ and which is unsubstituted or substituted byOR₁₁, SR₁₁ or N(R₁₂)(R₁₃);

or C₈-C₂₄arylcycloalkyl or C₈-C₂₄arylcycloalkenyl;

R₁₁ is H, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl orC₂-C₂₀alkyl which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted by OHand/or SH;

R₁₂ and R₁₃ independently of one another are hydrogen, C₁-C₂₀alkyl,C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl, which is interruptedonce or more than once by O or S and which is unsubstituted orsubstituted by OH and/or SH; or R₁₂ and R₁₃ together are C₃-C₅alkylenewhich is uninterrupted or interrupted by O, S or NR₁₄;

Z₁ is C₁-C₂₄alkyl which is unsubstituted or substituted once or morethan once by OR₁₅, SR₁₅, N(R₁₆)(R₁₇), phenyl, halogen, CN, —N═C═A,

or Z₁ is C₂-C₂₄alkyl which is interrupted once or more than once by O, Sor NR₁₄ and which can be substituted by OR₁₅, SR₁₅, N(R₁₆)(R₁₇), phenyl,halogen,

or Z₁ is C₁-C₂₄alkoxy, which is substituted once or more than once byphenyl, CN, —N═C═A,

or Z₁ is unsubstituted C₃-C₂₄cycloalkyl or C₃-C₂₄cycloalkyl substitutedby C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; unsubstituted C₂-C₂₄alkenyl orC₂-C₂₄alkenyl substituted by C₆-C₁₂aryl, CN, (CO)OR₁₅ or (CO)N(R₁₈)₂; orZ₁ is C₃-C₂₄cycloalkenyl or is one of the radicals

or Z₁ is C₁-C₂₄alkylthio, in which the alkyl radical is uninterrupted orinterrupted once or more than once by nonconsecutive O or S, and isunsubstituted or substituted by OR₁₅, SR₁₅ and/or halogen; with theproviso that Z₁ and R₆ are not identical;

A₁ is O, S or NR_(18a);

Z₂ is C₁-C₂₄alkylene; C₂-C₂₄alkylene interrupted once or more than onceby O, S or NR₁₄; C₂-C₂₄alkenylene; C₂-C₂₄alkenylene interrupted once ormore than once by O, S or NR₁₄; C₃-C₂₄cycloalkylene; C₃-C₂₄cycloalkyleneinterrupted once or more than once by O, S or NR₁₄; C₃-C₂₄cycloalkylene;C₃-C₂₄cycloalkenylene interrupted once or more than once by O, S orNR₁₄;

where the radicals C₁-C₂₄alkylene, C₂-C₂₄alkylene, C₂-C₂₄alkenylene,C₃-C₂₄cycloalkylene and C₃-C₂₄cycloalkenylene are unsubstituted or aresubstituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃) and/or halogen; or Z₂ is one ofthe radicals

where these radicals are unsubstituted or are substituted on thearomatic by C₁-C₂₀alkyl; C₂-C₂₀alkyl which is interrupted once or morethan once by nonconsecutive O atoms and which is unsubstituted orsubstituted by OH and/or SH; OR₁₁, SR₁₁, N(R₁₂)(R₁₃), phenyl, halogen,NO₂, CN, (CO)—OR₁₁, (CO)—R₁₁, (CO)—N(R₁₂)(R₁₃), SO₂R₂₄, OSO₂R₂₄, CF₃and/or CCl₃;

or Z₂ is a group

Z₃ is CH₂, CH(OH), CH(CH₃) or C(CH₃)₂;

Z₄ is S, O, CH₂, C═O, NR₁₄ or a direct bond;

Z₅ is S, O, CH₂, CHCH₃, C(CH₃)₂, C(CF₃)₂, SO, SO₂, CO;

Z₆ and Z₇ independently of one another are CH₂, CHCH₃ or C(CH₃)₂;

r is0, 1 or2;

s is a number from 1 to 12;

q is a number from 0 to 50;

t and p are each a number from 0 to 20;

E, G, G₃ and G₄ independently of one another are unsubstitutedC₁-C₁₂alkyl or C₁-C₁₂alkyl substituted by halogen, or are unsubstitutedphenyl or phenyl substituted by one or more C₁-C₄alkyl; or areC₂-C₁₂alkenyl;

R_(11a) is C₁-C₂₀alkyl substituted once or more than once by OR₁₅ or

or is C₂-C₂₀alkyl which is interrupted once or more than once bynonconsecutive O atoms and is unsubstituted or substituted once or morethan once by OR₁₅, halogen or

or R_(11a) is C₂-C₂₀alkenyl, C₃-C₁₂alkynyl; or R_(11a) isC₃-C₁₂cycloalkenyl which is substituted once or more than once byhalogen, NO₂, C₁-C₆alkyl, OR₁₁ or C(O)OR₁₈; or C₇-C₁₆arylalkyl orC₈-C₁₆arylcycloalkyl;

R₁₄ is hydrogen, phenyl, C₁-C₁₂alkoxy, C₁-C₁₂alkyl or C₂-C₁₂alkyl whichis interrupted once or more than once by O or S and which isunsubstituted or substituted by OH and/or SH;

R₁₅ has one of the meanings given for R₁₁ or is a radical

R₁₆ and R₁₇ independently of one another have one of the meanings givenfor R₁₂ or are a radical

R₁₈ is hydrogen, C₁-C₂₄alkyl, C₂-C₁₂alkenyl, C₃-C₈cycloalkyl, phenyl,benzyl; C₂-C₂₀alkyl which is interrupted once or more than once by O orS and which is unsubstituted or substituted by OH;

R_(18a) and R_(18b) independently of one another are hydrogen;C₁-C₂₀alkyl, which is substituted once or more than once by OR₁₅,halogen, styryl, methylstyryl, —N═C═A or

or C₂-C₂₀alkyl, which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted once ormore than once by OR₁₅, halogen, styryl, methylstyryl or

or R_(18a) and R_(18b) are C₂-C₁₂alkenyl; C₅-C₁₂cycloalkyl, which issubstituted by —N═C═A or —CH₂—N═C═A and is additionally unsubstituted orsubstituted by one or more C₁-C₄alkyl; or R_(18a) and R_(18b) areC₆-C₁₂aryl, unsubstituted or substituted once or more than once byhalogen, NO₂, C₁-C₆alkyl, C₂-C₄alkenyl, OR₁₁, —N═C═A, —CH₂—N═C═A orC(O)OR₁₈; or R_(18a) and R_(18b) are C₇-C₁₆arylalkyl; or R_(18a) andR_(18b) together are C₈-C₁₆arylcycloalkyl; or R_(18a) and R_(18b)independently of one another are

Y₃ is O, S, SO, SO₂, CH₂, C(CH₃)₂, CHCH₃, C(CF₃)₂, (CO), or a directbond;

R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ independently of one another are hydrogen,C₁-C₂₀alkyl;

C₂-C₂₀alkyl, which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted by OHand/or SH; or R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are OR₁₁, SR₁₁, N(R₁₂)(R₁₃),NO₂, CN, SO₂R₂₄, OSO₂R₂₄, CF₃, CCl3, halogen; or phenyl which isunsubstituted or substituted once or more than once by C₁-C₄alkyl orC₁-C₄alkoxy;

or in each case two of the radicals R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ togetherform C₁-C₂₀alkylene which is uninterrupted or interrupted by O, S or—NR₁₄;

R₂₄ is C₁-C₁₂alkyl, halogen-substituted C₁-C₁₂alkyl, phenyl, or phenylsubstituted by OR₁₁ and/or SR₁₁;

with the proviso that R₆ and Z₁ are not identical.

In the compounds of the formula III the preferred meanings for theradicals Ar, R₁, R₂, R₃, R₄, R₅ and R₆ are analogous to those givenabove for the compounds of the formula I.

A in formula III is, in particular, oxygen, x is preferably 1 and Ar ispreferably a group

Preference is given to compounds of the formula III, in which Ar is agroup

A is O; and x is 1; R₁ and R₂ independently of one another areC₁-C₁₂alkyl, C₁-C₁₂alkoxy, CF₃ or halogen; R₃, R₄ and R₅ independentlyof one another are hydrogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen; R₆ isC₁-C₁₂alkyl, unsubstituted or substituted by OR₁₁, cycloalkenyl, CN,C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, phenyl, cycloalkyl; C₂-C₁₂alkyl, whichis interrupted once or more than once by nonconsecutive O, S or NR₁₄ andwhich is unsubstituted or substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN,C(O)R₁₁, C(O)OR₁₁ and/or C(O)N(R₁₄)₂; C₂-C₁₂alkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); benzyl, cyclopentyl, cyclohexyl, C₄-C₁₂cycloalkyl which isuninterrupted or interrupted once or more than once by O, S and/or NR₁₄;or C₈-C₁₂arylcycloalkyl; R₁₂ and R₁₃ independently of one another arehydrogen, C₁-C₄alkyl, C₃-C₆cycloalkyl, phenyl, benzyl or C₂-C₁₂alkyl,which is interrupted once or more than once by O or S and which isunsubstituted or substituted by OH and/or SH, or R₁₂ and R₁₃ togetherare piperidino, morpholino or piperazino; Z₁ has the same meaning as R₆with the proviso that Z₁ and R₆ are not identical, or Z₁ isC₃-C₁₂cycloalkyl which is unsubstituted or substituted by C₁-C₂₀alkyl,OR₁₁, CF₃ or halogen; C₂-C₁₂alkenyl, or C₃-C₁₂cycloalkenyl, or Z₁ is oneof the radicals (g), (h), (i), (k), (l), (m), (n), (o), (p), (q), (t),(u), (v) or (w); Z₂ is C₁-C₁₈alkylene; C₂-C₁₂alkylene interrupted onceor more than once by O, S, or NR₁₄; C₂-C₁₂alkenylene; C₂-C₁₂alkenyleneinterrupted once or more than once by O, S, or NR₁₄;C₃-C₁₂Cycloalkylene; C₃-C₁₂cycloalkylene interrupted once or more thanonce by O, S, or NR₁₄; C₃-C₁₂cycloalkenylene; C₃-C₁₂cycloalkenyleneinterrupted once or more than once by O, S, or NR₁₄; where the radicalsC₁-C₁₈alkylene, C₂-C₁₂alkylene, C₂-C₁₂alkenylene, C₃-C₁₂cycloalkyleneand C₃-C₁₂cycloalkenylene are unsubstituted or substituted by OR₁₁,SR₁₁, N(R₁₂)(R₁₃) and/or halogen; or Z₂ is one of the radicals

where these radicals are unsubstituted or substituted on the aromatic byC₁-C₁₂alkyl; C₂-C₁₂alkyl, which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted by OHand/or SH; OR₁₁, SR₁₁, N(R₁₂)(R₁₃), phenyl, halogen, NO₂, CN, (CO)—OR₁₈,(CO)—R₁₈, (CO)—N(R₁₈)₂, SO₂R₂₄, and/or CF₃; or Z₂ is a group (r); Z₃ isCH₂, CHCH₃ or C(CH₃)₂; Z₄ is S, O, CH₂, C═O, NR₁₄ or a direct bond; Z₅is S, O, CH₂, CHCH₃, C(CH₃)₂, C(CF₃)₂, SO, SO₂; Z₆ and Z₇ independentlyof one another are CH₂, CHCH₃ or C(CH₃)₂; r is 0, 1 or 2; s is a numberfrom 1 to 12; q is a number from 0 to 50; t and p are each numbers from0 to 20; E, G, G₃ and G₄ independently of one another are C₁-C₁₂alkyl,or phenyl which is unsubstituted or substituted by one or moreC₁-C₄alkyl; R₁₄ is hydrogen, phenyl, C₁-C₄alkyl or C₁-C₄alkoxy; R₁₉,R₂₀, R₂₁, R₂₂ and R₂₃ have one of the meanings given for R₆ or are NO₂,CN, SO₂R₂₄, CF₃, or halogen; R₂₄ is C₁-C₁₂alkyl, halogen-substitutedC₁-C₁₂alkyl, phenyl, or OR₁₁- and/or SR₁₁-substituted phenyl.

Preferred R₆ are as given above for formula I.

R₁₂ and R₁₃ in the compounds of the formula III are preferablyC₁-C₄alkyl, C₁-C₄alkoxy or R₁₂ and R₁₃ together form a morpholino ring.

Also of interest are compounds of the formula III, in which Ar is agroup

A is O; and x is 1; R₁ and R₂ independantly of one another areC₁-C₄alkyl, C₁-C₄alkoxy, CF₃ or halogen; R₃, R₄ and R₅ independently ofone another are hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or chlorine; R₆ isC₁-C₁₂alkyl unsubstituted or substituted by OR₁₁, cycloalkenyl, CN,C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, phenyl, cycloalkyl; C₂-C₁₂alkyl which isinterrupted once or more than once by nonconsecutive O, S or NR₁₄ andwhich is unsubstituted or substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN,C(O)R₁₁, C(O)OR₁₁ and/or C(O)N(R₁₄)₂; C₂-C₁₂alkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); benzyl, cyclopentyl, cyclohexyl, C₄-C₁₂cycloalkyl which isuninterrupted or interrupted once or more than once by O, S and/or NR₁₄;or C₈-C₁₂arylcycloalkyl; R₁₁ is H, C₁-C₈alkyl, cyclopentyl, cyclohexyl,phenyl, benzyl or C₂-C₆alkyl which is interrupted once or twice bynonconsecutive O atoms and which is unsubstituted or substituted by OH;R₁₂ and R₁₃ independently of one another are hydrogen, C₁-C₄alkyl,cyclopentyl, cyclohexyl, phenyl, benzyl or C₂-C₆alkyl which isinterrupted once or twice by O and which is unsubstituted or substitutedby OH; or R₁₂ and R₁₃ together are morpholino; Z₁ has the same meaningas R₆ with the proviso that Z₁ and R₆ are not identical; or Z₁ is one ofthe radicals (g), (h), (i), (k), (l), (m), (n), (o), (p), (q), (t), (u),(v) or (w); Z₂ is C₁-C₁₂alkylene; C₂-C₁₂alkylene interrupted once ormore than once by O; C₂-C₁₂alkenylene; C₂-C₁₂alkenylene interrupted onceor more than once by O; C₅-C₈cycloalkylene; C₃-C₅cycloalkyleneinterrupted by O, S, or NR₁₄; C₅-C₈cycloalkenylene; C₃-C₅cycloalkenyleneinterrupted by O, S, or NR₁₄; where the radicals C₁-C₁₂alkylene,C₂-C₁₂alkylene, C₂-C₁₂alkenylene, C₅-C₈cycloalkylene andC₃-C₈cycloalkenylene are unsubstituted or substituted by OR₁₁; or Z₂ isone of the radicals

where these radicals are unsubstituted or substituted on the aromatic byC₁-C₄alkyl, OR₁₁, phenyl, (CO)—OR₁₈, (CO)—R₁₈ and/or (CO)—N(R₁₈)₂; or Z₂is a group (r); Z₃ is CH₂, CHCH₃ or C(CH₃)₂; Z₄ is S, O, CH₂, C═O, NR₁₄or a direct bond; Z₅ is O, CH₂, CHCH₃, C(CH₃)₂, C(CF₃)₂; Z₆ and Z₇independently of one another are CH₂, CHCH₃ or C(CH₃)₂; r is 0, 1 or 2;s is a number from 1 to 12; q is a number from 0 to 50; t and p in eachcase are a number from 0 to 20; E, G, G₃ and G₄ independently of oneanother are C₁-C₁₂alkyl, or phenyl which is unsubstituted or substitutedby one or more C₁-C₄alkyl; R₁₄ is hydrogen, phenyl or C₁-C₄alkyl.

Examples of compounds of the formula III according to the invention are

2,4,6-trimethylbenzoyl-n-butylmethylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylethylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylpropylphosphine oxide,2,4,6-trimethylbenzoyl-di(n-butyl)phosphine oxide,2,4,6-trimethylbenzoyl-n-butylpentylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylhexylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylheptyl phosphine oxide,2,4,6-trimethylbenzoyl-n-butyyoctylphosphine oxide,2,4,6-trimethylbenzoyl-n-butyldodecylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylisopropylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylisobutylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylamyl phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-ethylhexyl)phosphine oxide,(2,4,6-trimethylbenzoyl)-(n-butyl)-(tert.-butyl)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(1-methylpropyl)phosphine oxide,2,4,6-trimethylbenzoyl-n-butylisopentylphosphine oxide,2,4,6-trimethylbenzoyl-n-butylmethoxyethoxyphosphine oxide,2,4,6-trimethylbenzoyl-n-butylbenzyl phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2,4,4-trimethylpentyl)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic methyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic ethylester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionicpropyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic pentylester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionichexyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic octyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic decyl ester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic dodecylester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionicisopropyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic isobutyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic amylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic-2-ethylhexylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic-tert-butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionicisopentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl-(2-propionicbenzyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-n-butyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic methyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic ethyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic propyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic butyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic pentyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic hexyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic octyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic decyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic dodecyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic isopropyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic isobutyl esterphosphine oxide, 2,4,6-trimethylbenzoyl-n-butylacetic amyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl(acetic 2-ethylhexylester)phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butyl(acetictert-butyl ester phosphine oxide, (2,4,6-trimethylbenzoyl)-n-butylacetic1-methylpropyl ester)phosphine oxide,2,4,6-trimethylbenzoyl-n-butylacetic isopentyl ester phosphine oxide,2,4,6-trimethylbenzoyl-n-butylacetic methoxyethoxy ester phosphineoxide, 2,4,6-trimethylbenzoyl-n-butylacetic benzyl ester phosphineoxide, (2,4,6-trimethylbenzoyl)-n-butyl(acetic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoyl-n-butylmethylphosphineoxide, 2,6-dimethoxybenzoyl-n-butylethylphosphine oxide,2,6-dimethoxybenzoyl-butyl-propylphosphine oxide,2,6-dimethoxybenzoyl-i-n-butylphosphine oxide,2,6-dimethoxybenzoyl-n-butylpentylphosphine oxide,2,6-dimethoxybenzoyl-n-butylhexylphosphine oxide,2,6-dimethoxybenzoyl-n-butylheptylphosphine oxide,2,6-dimethoxybenzoyl-n-butyloctylphosphine oxide,2,6-dimethoxybenzoyl-n-butyldodecylphosphine oxide,2,6-dimethoxybenzoyl-n-butylisopropylphosphine oxide,2,6-dimethoxybenzoyl-n-butylisobutylphosphine oxide,2,6-dimethoxybenzoyl-n-butylamylphosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-ethylhexyl)phosphine oxide,2,6-dimethoxybenzoyl-n-butyl-tert-butylphosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(1-methylpropyl)phosphine oxide,2,6-dimethoxybenzoyl-n-butylisopentylphosphine oxide,2,6-dimethoxybenzoyl-n-butylmethoxyethoxyphosphine oxide,2,6-dimethoxybenzoyl-n-butylbenzylphosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2,4,4-trimethylpentyl)phosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-propionic methyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic ethyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic propylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic butylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionicpentyl ester)phosphine oxide,(2,6-dimethoxy-benzoyl)-n-butyl-(2-propionic hexyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic octyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic decyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic dodecylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionicisopropyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-propionic isobutyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic amyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionic 2-ethylhexylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionictert-butyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionicisopentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl-(2-propionicbenzyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-n-butyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic methyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic ethyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic propyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic butyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic pentyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic hexyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic octyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic decyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic dodecyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic isopropyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic isobutyl esterphosphine oxide, 2,6-dimethoxybenzoyl-n-butylacetic amyl ester phosphineoxide, (2,6-dimethoxybenzoyl)-n-butyl(acetic 2-ethylhexylester)phosphine oxide, 2,6-dimethoxybenzoyl-n-butyl(acetic tert-butylester)phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl(acetic1-methylpropyl ester)phosphine oxide, 2,6-dimethoxybenzoyl-n-butylaceticisopentyl ester phosphine oxide, 2,6-dimethoxybenzoyl-n-butylaceticmethoxyethoxy ester phosphine oxide, 2,6-dimethoxybenzoyl-n-butylaceticbenzyl ester phosphine oxide, (2,6-dimethoxybenzoyl)-n-butyl(acetic2,4,4-trimethylpentyl ester)phosphine oxide,(2,4,6-trimethylbenzoylisobutylmethylphosphine oxide,2,4,6-trimethylbenzoylisobutylethylphosphine oxide,2,4,6-trimethylbenzoylisobutylpropylphosphine oxide,2,4,6-trimethylbenzoylisobutyl-(n-butyl)phosphine oxide,2,4,6-trimethylbenzoylisobutylpentylphosphine oxide,2,4,6-trimethylbenzoylisobutylhexylphosphine oxide,2,4,6-trimethylbenzoylisobutylheptylphosphine oxide,2,4,6-trimethylbenzoylisobutyloctylphosphine oxide,2,4,6-trimethylbenzoylisobutyldodecylphosphine oxide,2,4,6-trimethylbenzoylisobutylisopropylphosphine oxide,2,4,6-trimethylbenzoyl-di-isobutylphosphine oxide,2,4,6-trimethylbenzoylisobutylamylphosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-ethylhexyl)phosphine oxide,2,4,6-trimethylbenzoylisobutyl(tert-butyl)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(1-methylpropyl)phosphine oxide,2,4,6-trimethylbenzoylisobutylisopentylphosphine oxide,2,4,6-trimethylbenzoylisobutylmethoxyethoxyphosphine oxide,2,4,6-trimethylbenzoylisobutylbenzylphosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2,4,4-trimethylpentyl)phosphine oxide,2,4,6-trimethylbenzoyl)isobutyl-(2-propionic methyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic ethylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl(2-propionicpropyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic pentylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionichexyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic octyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic decylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl(2-propionicdodecyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic isopropyl ester)phosphineoxide, (2,4,6-trimethyl benzoyl)isobutyl-(2-propionic isobutyl ester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic amylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic2-ethyahexyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic tert-butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionicisopentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl-(2-propionicbenzyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic methyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic ethyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic propyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic butyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic pentyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic hexyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic octyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic decyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic dodecyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic isopropyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic isobutyl esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic amyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl(acetic 2-ethylhexylester)phosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl(acetictert-butyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)isobutyl(acetic 1-methylpropyl ester)phosphineoxide, 2,4,6-trimethylbenzoylisobutylacetic isopentyl ester phosphineoxide, 2,4,6-trimethylbenzoylisobutylacetic methoxyethoxy esterphosphine oxide, 2,4,6-trimethylbenzoylisobutylacetic benzyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)isobutyl(acetic2,4,4-trimethylpentyl ester)phosphine oxide,2,6-dimethoxybenzoylisobutylmethylphosphine oxide,2,6-dimethoxybenzoylisobutylethylphosphine oxide,2,6-dimethoxybenzoylisobutylpropylphosphine oxide,2,6-dimethoxybenzoylisobutyl-(n-butyl)phosphine oxide,2,6-dimethoxybenzoylisobutylpentylphosphine oxide,2,6-dimethoxybenzoylisobutylhexylphosphine oxide,2,6-dimethoxybenzoylisobutylheptylphosphine oxide,2,6-dimethoxybenzoylisobutyloctylphosphine oxide,2,6-dimethoxybenzoylisobutyldodecylphosphine oxide,2,6-dimethoxybenzoylisobutylisopropylphosphine oxide,2,6-dimethoxybenzoyldi-isobutylphosphine oxide,2,6-dimethoxybenzoylisobutylamylphosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-ethylhexyl)phosphine oxide,2,6-dimethoxybenzoylisobutyl(tert-butyl)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(1-methylpropyl)phosphine oxide,2,6-dimethoxybenzoylisobutylisopentylphosphine oxide,2,6-dimethoxybenzoylisobutylmethoxyethoxyphosphine oxide,2,6-dimethoxybenzoylisobutylbenzylphosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2,4,4-trimethylpentyl)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic methyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic ethyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic propylester)phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic butylester)phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionicpentyl ester) phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic hexyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic octyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic decyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic dodecyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic isopropylester)phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionicisobutyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic amyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic 2-ethylhexyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic tert-butylester)phosphine oxide, (2,6-dimethoxybenzoy)isobutyl-(2-propionic1-methylpropyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic isopentyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl-(2-propionicbenzyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)isobutyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoyl-isobutylacetic methyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic ethyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic propyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic butyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic pentyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic hexyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic octyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic decyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic dodecyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic isopropyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic isobutyl esterphosphine oxide, 2,6-dimethoxybenzoylisobutylacetic amyl ester phosphineoxide, (2,6-dimethoxybenzoyl)-isobutyl(acetic 2-ethylhexylester)phosphine oxide, 2,6-dimethoxybenzoylisobutylacetic tert-butylester phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl(acetic1-methylpropyl ester)phosphine oxide, 2,6-dimethoxybenzoylisobutylaceticisopentyl ester phosphine oxide, 2,6-dimethoxybenzoylisobutylaceticmethoxyethoxy ester phosphine oxide, 2,6-dimethoxybenzoylisobutylaceticbenzyl ester phosphine oxide, (2,6-dimethoxybenzoyl)isobutyl(acetic2,4,4-trimethylpentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)methylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)ethylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)propylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)butylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)pentylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)hexylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)heptylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)octylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)dodecylphosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)isopropylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)isobutylphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-amylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-ethylhexy)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(tert-butyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(1-methylpropyl)phosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)isopentylphosphineoxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)methoxyethoxyphosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)benzylphosphineoxide, (2,4,6-trimethylbenzoyl)-bis(2,4,4-trimethylpentyl)phosphineoxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionicmethyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic ethylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic propylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic butylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic pentylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic hexylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic octylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic decylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic dodecylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isopropylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isobutylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic amylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic2-ethylhexyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic tert-butylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic1-methylpropyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isopentylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionicmethoxyethoxy ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic benzylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic2,4,4-trimethylpentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic methyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticethyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic propyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticbutyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic pentyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-acetichexyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic octyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticdecyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic dodecyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticisopropyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic isobutyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticamyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)(acetic 2- ethy hexylester) phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)(acetic tert-butylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)(acetic 1-methyl-propylester)phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic isopentyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)aceticmethoxyethoxy ester phosphine oxide,(2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)acetic benzyl esterphosphine oxide, (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)(acetic2,4,4-trimethylpentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)methylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)ethylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)propylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)butyl-phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)pentylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)hexylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)heptylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-octylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)dodecylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)isopropylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)isobutylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)amylphosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-ethylhexyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(tert-butyl)phosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(1-methylpropyl)phosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)isopentylphosphineoxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)methoxyethoxyphosphineoxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)benzylphosphineoxide, (2,6-dimethoxybenzoyl)-bis(2,4,4-trimethylpentyl)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic methylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic ethylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic propylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic butylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic pentylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic hexylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic octylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic decylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic dodecylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isopropylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isobutylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic amylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic 2-ethylhexylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic tert-butylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic1-methylpropyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic isopentylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionicmethoxyethoxy ester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic benzylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-(2-propionic2,4,4-trimethylpentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic methyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticethyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic propyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticbutyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic pentyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetichexyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic octyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticdecyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic dodecyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticisopropyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic isobutyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticamyl ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)(acetic 2-ethylhexylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)(acetic tert-butylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)(acetic 1-methylpropylester)phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic isopentyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)aceticmethoxyethoxy ester phosphine oxide,(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)acetic benzyl esterphosphine oxide, (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)(acetic2,4,4-trimethylpentyl ester)phosphine oxide,(2,4,6-trimethylbenzoylcyclopentylmethylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylethylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylpropylphosphine oxide, 2,4,6-trimethylbenzoylcyclopentylbutylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylpentylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylhexylphosphine oxide, 2,4,6-trimethylbenzoylcyclopentylheptylphosphine oxide,2,4,6-trimethylbenzoylcyclopentyloctylphosphine oxide,2,4,6-trimethylbenzoylcyclopentyldodecylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylisopropyl phosphine oxide,2,4,6-trimethylbenzoylcyclopentylisobutylphosphine oxide,2,4,6-trimethylbenzoylcyclopentylamylphosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-ethylhexyl)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(tert-butyl)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(1-methylpropyl)phosphine oxide,2,4,6-trimethylbenzoylcyclopentylisopentyyphosphine oxide,2,4,6-trimethylbenzoylcyclopentylmethoxyethoxyphosphine oxide,2,4,6-trimethylbenzoylcyclopentylbenzyl phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2,4,4-trimethylpentyl)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic methyl ester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic ethylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionicpropyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic pentylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionichexyl ester)phosphineoxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic octyl ester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic decylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionicdodecyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic isopropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionicisobutyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic amyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic 2-ethylhexylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionictert-butyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionicisopentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionicbenzyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic methylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic ethylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic propylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic butylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic pentylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic hexylester phosphine oxide, 2,4,6-trimethyl-benzoylcyclopentylacetic octylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic decylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic dodecylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic isopropyester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic isobutylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic amylester phosphine oxide, (2,4,6-trimethylbenzoyl)cyclopentyl(acetic2-ethylhexyl ester)phosphine oxide,2,4,6-trimethylbenzoylcyclopentyl(acetic tert-butyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclopentylacetic 1-methylpropylester)phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylacetic isopentylester phosphine oxide, 2,4,6-trimethylbenzoylcyclopentylaceticmethoxyethoxy ester phosphine oxide,2,4,6-trimethylbenzoylcyclopentylacetic benzyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)cyclopentyl(acetic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoylcyclopentylmethylphosphineoxide, 2,6-dimethoxybenzoylcyclopentylethylphosphine oxide,2,6-dimethoxybenzoylcyclopentylpropylphosphine oxide,2,6-dimethoxybenzoylcyclopentylbutylphosphine oxide,2,6-dimethoxybenzoylcyclopentylpentylphosphine oxide,2,6-dimethoxybenzoylcyclopentylhexylphosphine oxide,2,6-dimethoxybenzoylcyclopentylheptylphosphine oxide,2,6-dimethoxybenzoylcyclopentyloctylphosphine oxide,2,6-dimethoxybenzoylcyclopentyldodecylphosphine oxide,2,6-dimethoxybenzoylcyclopentylisopropylphosphine oxide,2,6-dimethoxybenzoylcyclopentylisobutylphosphine oxide,2,6-dimethoxybenzoylcyclopentylamylphosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-ethylhexyl)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(tert-butyl)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(1-methylpropyl)phosphine oxide,2,6-dimethoxybenzoylcyclopentylisopentylphosphine oxide,2,6-dimethoxybenzoylcyclopentylmethoxyethoxyphosphine oxide,2,6-dimethoxybenzoylcyclopentylbenzylphosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2,4,4-trimethylpentyl)phosphineoxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic methylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicethyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic propyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic butylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicpentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic hexyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic octylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicdecyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic dodecyl ester) phosphineoxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic isopropylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicisobutyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic amyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic 2-ethylhexylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionictert-butyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic 1-methylpropyl ester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicisopentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl-(2-propionicbenzyl ester) phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoylcyclopentyl-acetic methylester phosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic ethyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic propyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic butyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic pentyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic hexyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic octyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic decyl esterphosphine oxide, 2,6-dimethoxybenzoyl-cyclopentylacetic dodecyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic isopropyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic isobutyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic amyl esterphosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl(acetic 2-ethylhexylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl(acetictert-butyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclopentyl(acetic 1-methylpropyl ester)phosphineoxide, 2,6-dimethoxybenzoylcyclopentylacetic isopentyl ester phosphineoxide, 2,6-dimethoxybenzoylcyclopentylacetic methoxyethoxy esterphosphine oxide, 2,6-dimethoxybenzoylcyclopentylacetic benzyl esterphosphine oxide, (2,6-dimethoxybenzoyl)cyclopentyl(acetic2,4,4-trimethylpentyl ester)phosphine oxide,2,4,6-trimethylbenzoylcyclohexylmethylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylethylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylpropylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylbutylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylpentylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylhexylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylheptylphosphine oxide,2,4,6-trimethylbenzoylcyclohexyloctylphosphine oxide,2,4,6-trimethylbenzoylcyclohexyldodecylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylisopropylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylisobutylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylamylphosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-ethylhexyl)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl(tert.-butyl)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(1-methylpropyl)phosphine oxide,2,4,6-trimethylbenzoylcyclohexylisopentylphosphine oxide,2,4,6-trimethylbenzoylcyclohexylmethoxyethoxyphosphine oxide,2,4,6-trimethylbenzoylcyclohexylbenzylphosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2,4,4-trimethylpentyl)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic methylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionicethyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic propyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic butylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionicpentyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic hexyl ester) phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic octylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionicdecyl ester) phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic dodecyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic isopropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionicisobutyl ester) phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic amyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic 2-ethylhexylester)phosphine oxide, (2,4,6-trimethylbenzoylcyclohexyl-(2-propionictert-butyl ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionicisopentyl ester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic methoxyethoxy ester)phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic benzyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl-(2-propionic2,4,4-trimethylpentyl ester)phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic methyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic ethyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic propyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic butyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic pentyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic hexyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic octyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic decyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic dodecyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic isopropyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic isobutyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic amyl ester phosphine oxide,(2,4,6-trimethylbenzoyl)cyclohexyl(acetic 2-ethylhexyl ester)phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl(acetic tert-butylester)phosphine oxide, (2,4,6-trimethylbenzoyl)cyclohexyl(acetic1-methylpropyl ester)phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic isopentyl ester phosphine oxide,2,4,6-trimethylbenzoylcyclohexylacetic methoxyethoxy ester phosphineoxide, 2,4,6-trimethylbenzoylcyclohexylacetic benzyl ester phosphineoxide, (2,4,6-trimethylbenzoyl)cyclohexyl(acetic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoylcyclohexylmethylphosphineoxide, 2,6-dimethoxybenzoylcyclohexylethylphosphine oxide,2,6-dimethoxybenzoylcyclohexylpropylphosphine oxide,2,6-dimethoxybenzoylcyclohexylbutylphosphine oxide,2,6-dimethoxybenzoylcyclohexylpentylphosphine oxide,2,6-dimethoxybenzoylcyclohexylhexylphosphine oxide,2,6-dimethoxybenzoylcyclohexylheptylphosphine oxide,2,6-dimethoxybenzoylcyclohexyloctylphosphine oxide,2,6-dimethoxybenzoylcyclohexyldodecylphosphine oxide,2,6-dimethoxybenzoylcyclohexylisopropylphosphine oxide,2,6-dimethoxybenzoylcyclohexylisobutylphosphine oxide,2,6-dimethoxybenzoylcyclohexylamylphosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-ethylhexyl)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(tert-butyl)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(1-methylpropyl)phosphine oxide,2,6-dimethoxybenzoylcyclohexylisopentylphosphine oxide,2,6-dimethoxybenzoylcyclohexylmethoxyethoxyphosphine oxide,2,6-dimethoxybenzoylcyclohexylbenzylphosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2,4,4-trimethylpentyl)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic methyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic ethylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionicpropyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic butyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic pentylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionichexyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic octyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic decylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionicdodecyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic isopropyl ester)phosphineoxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic isobutylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionicamyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic 2-ethylhexylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionictert-butyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic 1-methylpropylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionicisopentyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic methoxyethoxyester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl-(2-propionicbenzyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl-(2-propionic 2,4,4-trimethylpentylester)phosphine oxide, 2,6-dimethoxybenzoyl-cyclohexylacetic methylester phosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic ethyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic propyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic butyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic pentyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic hexyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic octyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic decyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic dodecyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic isopropyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic isobutyl esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic amyl esterphosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl(acetic 2-ethylhexylester)phosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl(acetictert-butyl ester)phosphine oxide,(2,6-dimethoxybenzoyl)cyclohexyl(acetic 1-methylpropyl ester)phosphineoxide, 2,6-dimethoxybenzoylcyclohexylacetic isopentyl ester phosphineoxide, 2,6-dimethoxybenzoylcyclohexylacetic methoxyethoxy esterphosphine oxide, 2,6-dimethoxybenzoylcyclohexylacetic benzyl esterphosphine oxide, (2,6-dimethoxybenzoyl)cyclohexyl(acetic2,4,4-trimethylpentyl ester)phosphine oxide.

The compounds of the formula III are obtained by reaction of acorresponding compound of the formula I with a compound Z₁—X (VI), wherefirstly the compound of the formula III in which x=0 (III′) is prepared:

Ar, M, X, and R₆ are as defined above and in the claims. Z₁′ has themeanings as given in claim 1, with the exception of the groups (v), (w)and C₁-C₂₄alkylthio. (The preparation of compounds of the formula III inwhich Z₁ is (v), (w) or C₁-C₂₄alkylthio is described below.) Ifcompounds of the formula III where A═O or S are to be prepared, anoxidation or sulfurization of the compound of the formula (III′) is thencarried out, either after the compounds of the formula (III′) have beenseparated off by customary methods, or without isolation thereof. Theconditions for such reactions are analogous to those described for thepreparation of the compounds of the formula II.

If a compound of the formula (III) in which Z₁ is a radical

in which Z₁ C₁-C₂₄alkylthio, then the compound of the formula (I) isreacted with a compound of the formula Z₁—SO₂—X, where, without anintermediate stage, a compound of the formula (III) where A═O and x=1 isdirectly obtained. (Z₁ is defined as above, X is defined as in theclaims.) The carrying out of the oxidation step is thereforeunnecessary.

Similar reactions are described, for example, in Houben-Weyl, E2,Methoden der Organischen Chemie, 4^(th) edition, pages 222-225.

If compounds of the formula (III) in which Z₁ is a radical (v) or (w) orC₁-C₂₄alkylthio and in which A is sulfur are to be prepared, then it is,for example, possible to convert the corresponding oxide compound asdescribed above into the sulfide. This is possible, for example, byreacting the corresponding phosphine oxide with an excess of P₂S₅ orelemental sulfur in a high-boiling solvent. Such reactions, i.e.reactions in which a P═O bond is converted into a P═S bond, aredescribed, for example, in L. Horner et al., Chem. Ber. 92, 2088 (1959)and U.S. Pat. No. 2,642,461. In principle, it is also possible tofirstly reduce the corresponding phosphine oxide compound to give therespective phosphine and then to sulfurize the phosphine. I.e. the P═Obond is reduced to give the phosphine using a suitable reducing agent,and is then sulfurized with elemental sulfur to give the P═S bond.Reducing agents which may be used are, for example, LiAlH₄, Ca(AlH₄)₂,CaH₂, AlH₃, SiHCl₃, PhSiH₃ and the agents as described in “OrganicPhosphorous Compounds, Wiley-Interscience 1972, Vol. 1, pages 45-46 andVol.3, pages 408-413”.

The invention provides a process for the preparation of compounds of theformula III from the novel starting materials of the formula I,

(1) by reaction of an acyl halide of the formula IV

in which

Ar is as defined above, and

X is Cl or Br;

with a dimetalated organophosphine of the formula V

in which

R₆ is as defined above; and

M₁ is Na, Li or K;

in the molar ratio of approximately 1:1;

(2) subsequent reaction of the product with a compound of the formula VIor VI′

Z₁═  (VI)

Z₁—X′  (VI′),

in which

Z₁ is as defined above; and

X is as defined above; and

X′ —N═C═A, —N═C═N═Z₁,

or —CHO;

with the proviso that Z, is not identical to R₆;

in the molar ratio of approximately 1:1; and,

(3) in the case where Z₁ is not a group (v), (w) or C₁-C₁₂alkylthio andcompounds of the formula III in which A is oxygen or sulfur are to beobtained, subsequent oxidation or sulfurization of the resultingphosphine compounds.

The invention also provides a process for the preparation of compoundsof the formula III

(1) by reaction of an acyl halide of the formula IV

in which

Ar is as defined above, and

X is Cl or Br;

with an unsymmetrical phosphine of the formula VII

in which

R₆ is as defined above, and

Z₁ is as defined above with the proviso that R₆ and Z₁ are notidentical;

in the molar ratio of approximately 1:1, in the presence of a base or anorganolithium compound, to give the corresponding acylphosphine; and

(2) subsequent oxidation or sulfurization of the acylphosphine thusobtained.

This preparation process is novel and likewise provided by theinvention.

Suitable bases for this process are, for example, organolithiumcompounds, such as butyllithium, or organic nitrogen bases, for exampletertiary amines or pyridine.

Furthermore, the compounds of the formula III can also be prepared byreacting the compound of the formula I with phosgene, analogous to thedescription in “W. A. Henderson et al., J. Am. Chem. Soc. 1960, 82,5794” or “GB 904 086” or in “Organic Phosphorous Compounds, Editors: R.M. Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.1, page 28” or“Houben-Weyl, Methoden der Organischen Chemie, Vol. XII/1, page 201” togive the corresponding phosphine chloride (Ii). Compounds of the formula(Ii) can, as described in “Organic Phosphorous Compounds, Editors: R. M.Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.4, pages 268-269”,be reacted with alcohols to give compounds of the formula (Iii), whichare then directly reacted with an organohalide of the formula VI, inanalogy to “K. Sasse in Houben-Weyl, Methoden der Organischen Chemie,Vol XII/1, page 433” (by Michaelis-Arbuzov reaction), to give compoundsof the formula III. In this case, the oxidation or sulfurization step issuperfluous.

Ar are Z₁ are as described in claim 1 and 3; X is Cl or Br; R₆ and M arelikewise defined as in claim 1, and R is any alcohol radical, e.g.C₁-C₁₂alkyl, C₅-C₈cycloalkyl, for example cyclopentyl or cyclohexyl, orbenzyl.

The reaction conditions for the reaction of the compounds of the formula(I)→formula (Ii)→formula (Iii) are analogous to those described abovefor the preparation of the compounds of the formula (II) by thisprocess.

The conversion of compounds of the formula (Iii) to compounds of theformula (III) is carried out by adding corresponding alkyl halides(Z₁—X) to a solution of compounds of the formula (Iii) in in an inertsolvent. Here, the alkyl halide is advantageously dissolved, forexample, in the same solvent. The addition is carried out, for example,at a temperature of from 40° C. to 140° C., preferably at 60° C. to 120°C., the lower-boiling alkyl halide (RX) liberated during the reactionadvantageously being removed from the reaction solution by distillation.Solvents which may be used are e.g. alkanes, such as hexane, octane;cycloalkanes, such as cyclohexane; ethers, such as tert-butyl methylether, tetrahydrofuran, dioxane; or aromatic solvents, such as tolueneor xylene. The compounds of the structure (III) are isolated andpurified, for example, by distillation under reduced pressure,crystallization or by chromatography.

Compounds of the formula (Iii) can be oxidized using suitable oxidizingagents, such as peroxo acids, hydrogen peroxide or hydrogenperoxide/urea to give the corresponding phosphinic esters (Iiii):

The invention thus also provides a process for the preparation ofcompounds of the formula III in which A is oxygen and x is 1, by

(1) reaction of a compound of the formula (I),

in which

Ar, M and R₆ are as defined above,

with phosgene to give corresponding phosphine chloride (Ii)

(2) subsequent reaction with an alcohol to give the compound of theformula (Iii)

R is the radical of an alcohol, in particular C₁-C₁₂alkyl,C₅-C₈cycloalcyl or benzyl; and

(3) reaction of the resulting compound of the formula (Iii) with anorganohalide

Z₁—X,

in which

Z₁ is as defined above, but is not identical to R₆ from the formula (I),and

X is Cl or Br,

to give the compound of the formula III.

It is also conceivable to obtain the compounds of the formula IIIaccording to the invention by another method. E.g. processes asdescribed in U.S. Pat. No.4,298,738 or U.S. Pat. No. 4,324,744 could beused.

The invention provides for the use of compounds of the formula I asstarting materials for the preparation of mono- or bisacylphosphines,mono- or bisacylphosphine oxides or mono- or bisacylphosphine sulfides.

Preference is also given to compounds of the formula I, II and III, inwhich

Ar is a group

A is O;

x is 1;

R₁ and R₂ are methyl;

R₃ is methyl;

R₄ and R₅ are hydrogen;

R₆ is C₁-C₄alkyl;

M is Li;

Z₁ is a radical

Z₃ is CH₂; and

R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are hydrogen

Preference is given, in particular, to compounds of the formula I, IIand III

in which

Ar is a group

R₁ and R₂ independently of one another are C₁-C₈alkyl or OR₁₁;

R₃, R₄ and R₅ independently of one another are hydrogen or C₁-C₈alkyl;

R₆ is C₁-C₁₂alkyl;

R₁₁ is H or C₁-C₈alkyl;

R₁₂ and R₁₃ independently of one another are hydrogen or C₁-C₈alkyl;

M is hydrogen or Li;

A is O;

x is 1;

Y₁ is OR₁₁, N(R₁₂)(R₁₃) or a radical

R₁′ and R₂′ independently of one another have the same meanings givenfor R₁ and R₂; and

R₃′, R₄′ and R₅′ independently of one another have the same meanings asgiven for R₃, R₄ and R₅;

with the proviso that Y₁ is not identical to Ar;

Z₁ is C₁-C₁₂alkyl which is unsubstituted or substituted once or morethan once by OR₁₅, phenyl and/or

or Z₁ is unsubstituted or OR₁₁-substituted C₃-C₂₄cycloalkyl; or

Z₁ is one of the radicals

Z₃ is CH₂ or CH(OH);

r is 0;

s is 1;

E, G and G₃ independently of one another are unsubstituted C₁-C₄alkyl;

R₁₅ has one of the meanings given for R₁₁;

R₁₈ is C₁-C₁₂alkyl; and

R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ independently of one another are hydrogen orhalogen;

and with the proviso that R₆ and Z₁ are not identical.

According to the invention, the compounds of the formulae II and III canbe used as photoinitiators for the photopolymerization of ethylenicallyunsaturated compounds or mixtures which comprise such compounds.

This use can also take place in combination with another photoinitiatorand/or other additives.

The invention thus also relates to photopolymerizable compositionscomprising

(a) at least one ethylenically unsaturated photopolymerizable compoundand

(b) as photoinitiator, at least one compound of the formula II and/orIII,

where the composition, in addition to the component (b), can alsocomprise other photoinitiators (c) and/or other additives (d).

Preference is given to using in these compositions compounds of theformula II or III in which x is 1, in particular those compounds inwhich x is 1 and A is oxygen. Very particular preference is given insuch compositions to those compounds of the formula II and III, in whichAr is a group

A is oxygen and x is 1.

The unsaturated compounds can contain one or more olefinic double bonds.They can be of low molecular weight (monomeric) or relatively highmolecular weight (oligomeric). Examples of monomers with a double bondare alkyl or hydroxyalkyl acrylates or methacrylates, for example methylacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate orethyl methacrylate. Also of interest are silicon- or fluorine-modifiedresins, e.g. silicone acrylates. Further examples are acrylonitrile,acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinylesters, such as vinyl acetate, vinyl ethers, such as isobutyl vinylether, styrene, alkyl- and halostyrenes, N-vinylpyrrolidone, vinylchloride or vinylidene chloride.

Examples of monomers having two or more double bonds are ethylene glycoldiacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate,hexamethylene glycol diacrylate or bisphenol A diacrylate,4,4′-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate or tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanu rate or tris(2-acryloylethyl) isocyanurate.

Examples of higher molecular weight (oligomeric) polyunsaturatedcompounds are acrylicized epoxy resins, polyurethanes, polyethers andpolyesters which are acrylicized or contain vinyl ether or epoxy groups.Further examples of unsaturated oligomers are unsaturated polyesterresins which are mostly prepared from maleic acid, phthalic acid and oneor more diols and have molecular weights of from about 500 to 3,000. Inaddition, it is also possible to use vinyl ether monomers and oligomers,and maleate-terminated oligomers having polyester, polyurethane,polyether, polyvinyl ether and epoxy main chains. In particular,combinations of oligomers which carry vinyl ether groups and polymers asdescribed in WO 90/01512 are highly suitable. However, copolymers ofvinyl ether and maleic acid-functionalized monomers are also suitable.Such unsaturated oligomers may also be referred to as prepolymers.

Examples of particularly suitable compounds are esters of ethylenicallyunsaturated carboxylic acids and polyols or polyepoxides, and polymerscontaining ethylenically unsaturated groups in the chain or inside-groups, for example unsaturated polyesters, polyamides andpolyurethanes and copolymers thereof, alkyd resins, polybutadiene andbutadiene copolymers, polyisoprene and isoprene copolymers, polymers andcopolymers containing (meth)acrylic groups in side chains, and mixturesof one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fattyacids such as linolenic acid or oleic acid. Preference is given toacrylic acid and methacrylic acid.

Suitable polyols are aromatic and, in particular, aliphatic andcycloaliphatic polyols. Examples of aromatic polyols are hydroquinone,4,4′-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and alsonovolaks and resols. Examples of polyepoxides are those based on saidpolyols, particularly aromatic polyols and epichlorohydrins. Inaddition, polymers and copolymers which contain hydroxyl groups in thepolymer chain or in side groups, for example polyvinyl alcohol andcopolymers thereof or hydroxyalkyl polymethacrylates or copolymersthereof, are also suitable as polyols. Further suitable polyols areoligoesters containing hydroxyl end-groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving, preferably, 2 to 12 carbon atoms, such as ethylene glycol, 1,2-or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol,hexanediol, octanediol, dodecanediol, diethylene glycol, triethyleneglycol, polyethylene glycols having molecular weights of, preferably,200 to 1,500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(,-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may be partially or completely esterified using one ordifferent unsaturated carboxylic acids, where the free hydroxyl groupsin partial esters may be modified, e.g. etherified or esterified withother carboxylic acids.

Examples of esters are:

trimethylolpropane triacrylate, trimethylolethane triacrylate,trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate,tetraethylene glycol diacrylate, pentaerythritol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol diacrylate, dipentaerythritol triacrylate,dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate,pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,tripentaerythritol octamethacrylate, pentaerythritol diitaconate,dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate,dipentaerythritol hexaitaconate, ethylene glycol diacrylate,1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldiitaconate, sorbitol triacrylate, sorbitol tetraacrylate,pentaerythritol-modified triacrylate, sorbitol tetramethacrylate,sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates andmethacrylates, glycerol di- and triacrylate, 1,4-cyclohexane diacrylate,bisacrylates and bismethacrylates of polyethylene glycol havingmolecular weights of from 200 to 1,500, or mixtures thereof.

Also suitable as component (a) are the amides of identical or differentunsaturated carboxylic acids of aromatic, cycloaliphatic and aliphaticpolyamines having, preferably, 2 to 6, particularly 2 to 4, aminogroups. Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)ethane ordi(β-aminopropoxy)ethane. Further suitable polyamines are polymers andcopolymers with or without additional amino groups in the side chain andoligoamides containing amino end groups. Examples of such unsaturatedamides are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide,diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane,β-methacrylamidoethyl methacrylate, N[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and diols or diamines. Some of the maleic acid may bereplaced by other dicarboxylic acids. They can be used together withethylenically unsaturated comonomers, e.g. styrene. The polyesters andpolyamides may also be derived from dicarboxylic acids and ethylenicallyunsaturated diols or diamines, particularly from relatively long chaincompounds containing, for example, 6 to 20 carbon atoms. Examples ofpolyurethanes are those constructed from saturated or unsaturateddiisocyanates and unsaturated or saturated diols.

Polybutadiene and polyisoprene and copolymers thereof are known.Suitable comonomers are, for example, olefins, such as ethylene,propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene orvinyl chloride. Polymers containing (meth)acrylate groups in the sidechain are likewise known. These may, for example, be products of thereaction of novolak-based epoxy resins with (meth)acrylic acid, homo- orcopolymers of vinyl alcohol or hydroxyalkyl derivatives thereof whichhave been esterified using (meth)acrylic acid, or homo- and copolymersof (meth)acrylates which have been esterified using hydroxyalkyl(meth)acrylates.

The photopolymerizable compounds may be used on their own or in anydesired mixtures. Preference is given to using mixtures of polyol(meth)acrylates.

It is also possible to add binders to the compositions according to theinvention; this is particularly advantageous if the photopolymerizablecompounds are liquid or viscose substances. The amount of binder may,for example, be 5-95% by weight, preferably 10-90% by weight andparticularly 40-90% by weight, based on the total solids. The binder ischosen depending on the field of application and on the propertiesrequired therefore, such as the facility for development in aqueous ororganic solvent systems, adhesion to substrates and sensitivity tooxygen.

Examples of suitable binders are polymers having a molecular weight offrom about 5,000-2,000,000, preferably 10,000-1,000,000. Examples are:homo- and copolymeric acrylates and methacrylates, e.g. copolymers ofmethyl methacrylate/ethyl acrylate/methacrylic acid, poly(alkylmethacrylates), poly(alkyl acrylates); cellulose esters and celluloseethers, such as cellulose acetate, cellulose acetate butyrate,methylcellulose, ethylcellulose; polyvinylbutyral, polyvinylformal,cyclized rubber, polyethers, such as polyethylene oxide, polypropyleneoxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane,chlorinated polyolefins, polyvinyl chloride, copolymers of vinylchloride/vinylidene chloride, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene/vinyl acetate), polymers such as polycaprolactam andpoly(hexamethyleneadipamide), and polyesters such as poly(ethyleneglycol terephthalate) and poly(hexamethylene glycol succinate).

The unsaturated compounds can also be used in mixtures withnon-photopolymerizable film-forming components. These may, for example,be physically drying polymers or solutions thereof in organic solvents,for example nitrocellulose or cellulose acetobutyrate. However, they mayalso be chemically or thermally curable resins, for examplepolyisocyanates, polyepoxides or melamine resins. The co-use ofthermally curable resins is of importance for use in so-called hybridsystems, which are photopolymerized in a first stage and are crosslinkedby thermal aftertreatment in a second stage.

The photoinitiators according to the invention are also suitable asinitiators for the curing of oxidatively drying systems, as aredescribed, for example, in Lehrbuch der Lacke und Beschichtungen VolumeIII, 296-328, Verlag W. A. Colomb in Heenemann GmbH,Berlin-Oberschwandorf (1976).

Apart from the photoinitiator, the photopolymerizable mixtures can alsocontain various additives (d). Examples thereof are thermal inhibitors,which are intended to prevent premature polymerization, for examplehydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol orsterically hindered phenols, for example 2,6-di(tert-butyl)-p-cresol. Toincrease the storage stability in the dark it is possible, for example,to use copper compounds, such as copper naphthenate, stearate oroctoate, phosphorus compounds, for example triphenylphosphine,tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzylphosphite, quaternary ammonium compounds, for exampletetramethylammonium chloride or trimethylbenzylammonium chloride, orhydroxylamine derivatives, for example N-diethylhydroxylamine. In orderto exclude atmospheric oxygen during the polymerization, it is possibleto add paraffin or similar wax-like substances which migrate to thesurface at the start of the polymerization due to their lack ofsolubility in the polymers, and form a transparent surface layer whichprevents the entry of air. It is likewise possible to apply anoxygen-impermeable layer. Light protection agents which may be used areUV absorbers, for example those of the hydroxyphenylbenzotriazol,hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type.The compounds can be used individually or as mixtures, with or withoutthe use of sterically hindered amines (HALS).

Examples of such UV absorbers and light protection agents are

1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, mixtureof2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃]₂— whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl.

2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivatives.

3. Esters of unsubstituted or substituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

4. Acrylates, for example ethyl and isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl andbutyl α-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

5. Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(2,2,6,6-tetramethylpiperidyl) succinate,bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the product of thecondensation of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the product of the condensation ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,1,1′-(1,2-ethanediyl)bis-(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the product ofthe condensation ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the product of thecondensation of2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the product of the condensationof2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,the product of the condensation of2,4-bis[1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazineand N,N′-bis(3-aminopropyl)ethylenediamine.

6. Oxalamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and mixtures thereof with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide, and mixtures of o- andp-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

7. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,5-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand2-[4-dodecyl/tridecyloxy(2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

8. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkylphosphites, phenyl dialkylphosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bisisodecyloxy-pentaerythritoldi-phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritoldiphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritoldiphosphite, tristearylsorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl)-4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz[d,g]-1,3,2-dioxaphosphocine,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine,bis(2,4-di-tert-butyl-6-methylphenyl) methylphosphite, andbis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphite.

Examples of UV absorbers and light protection agents suitable ascomponent (d) are also “Krypto-UVA”, as are described, for example, inEP 180548. It is also possible to use latent UV absorbers, as described,for example, by Hida et al. in RadTech Asia 97, 1997, page 212.

It is also possible to use additives customary in the art, for exampleantistats, levelling auxiliaries and adhesion improvers.

To accelerate the photopolymerization it is possible to add, as furtheradditives (d), a large number of amines, for example triethanolamine,N-methyidiethanolamine, ethyl p-dimethylaminobenzoate or Michlersketone. The action of the amines can be intensified by the addition ofaromatic ketones, e.g. of the benzophenone type. Examples of amineswhich can be used as oxygen scavengers are substitutedN,N-dialkylanilines, as described in EP 339841.

Other accelerators, coinitiators and autoxidators are thiols,thioethers, disulfides and phosphines, as described, for example, in EP438123 and GB 2180358.

It is also possible to add chain transfer reagents customary in the artto the compositions according to the invention. Examples thereof aremercaptans, amines and benzothiazols.

The photopolymerization can also be accelerated by the addition ofphotosensitizers as further additives (d); these shift and/or broadenthe spectral sensitivity. These are, in particular, aromatic carbonylcompounds, for example benzophenone, thioxanthone, in particular alsoisopropylthioxanthone, anthraquinone and 3-acylcoumarin derivatives,terphenyls, styryl ketones, and 3-(aroylmethylene)thiazolines,camphorquinone, but also eosin, rhodamine and erythrosine dyes.

As photosensitizers, it is also possible, for example, to consider theamines given above. Further examples of such photosensitizers are

1. Thioxanthones

thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,2-dodecylthioxanthone, 2,4-diethylthioxanthone,2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone,2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone,4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone,1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone,1-ethoxycarbonyl-3-ethoxythioxanthone,1-ethoxycarbonyl-3-aminothioxanthone,1-ethoxycarbonyl-3-phenylsulfurylthioxanthone,3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone,1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone,2-methyl-6-dimethoxymethylthioxanthone,2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone,2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone,n-allylthioxanthone-3,4-dicarboximide,n-octylthioxanthone-3,4-dicarboximide,N-(1,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboximide,1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone,6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethyleneglycol ester,2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-1-propanaminiumchloride;

2. Benzophenones

benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone,4,4′-dimethoxybenzophenone, 4,4′-dimethylbenzophenone,4,4′-dichlorobenzophenone, 4,4′-dimethylaminobenzophenone,4,4′-diethylaminobenzophenone, 4-methylbenzophenone,2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)benzophenone,3,3′-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate,4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone,4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride,2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloridemonohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)benzophenone,4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethylbenzenemethanaminiumchloride;

3. 3-Acylcoumarins

3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin,3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichlorocoumarin,3-benzoyl-6-chlorocoumarin, 3,3′-carbonylbis[5,7-di(propoxy)coumarin],3,3′-carbonylbis(7-methoxycoumarin),3,3′-carbonylbis(7-diethylaminocoumarin), 3-isobutyroylcoumarin,3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin,3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di(methoxyethoxy)coumarin,3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin,3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin,5,7-dimethoxy-3-(1-naphthoyl)coumarin,5,7-dimethoxy-3-(1-naphthoyl)coumarin, 3-benzoylbenzo[f]coumarin,7-diethylamino-3-thienoylcoumarin,3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin;

4. 3-(Aroylmethylene)thiazolines

3-Methyl-2-benzoylmethylene-β-naphthothiazoline,3-methyl-2-benzoylmethylenebenzothiazoline,3-ethyl-2-propionylmethylene-β-naphthothiazoline;

5. Other carbonyl compounds

Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil,2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone,dibenzosuberone, xanthone,2,5-bis(4-diethylaminobenzylidene)cyclopentanone,α-(para-dimethylaminobenzylidene) ketones, such as2-(4-dimethylaminobenzylidene)indan-1-one or3-(4-dimethylaminophenyl)-1-indan-5-ylpropenone,3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthalimide.

The curing process can also be aided, in particular, by pigmentedcompositions (e.g. with titanium dioxide), also by the addition asadditional additive (d) of a component which forms the radicals underthermal conditions, for example an azo compound, such as2,2′-azobis-(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for example hydroperoxide orperoxycarbonate, e.g. t-butyl hydroperoxide, as described, for example,in EP 245639.

As further additive (d), the compositions according to the invention canalso comprise a photoreproducible dye, for example xanthene,benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin oracridine dyes, and/or a radiation-cleavable trihalomethyl compound.Similar compositions are described, for example, in EP 445624.

Depending on the intended use, further customary additives (d) areoptical brighteners, fillers, pigments, both white and colouredpigments, dyes, antistats, wetting agents or levelling auxiliaries.

For the curing of thick and pigmented coatings, the addition ofmicroglass beads or pulverized glass fibres, as described, for example,in U.S. Pat. No. 5,013,768, is suitable.

The formulations can also comprise dyes and/or white or colouredpigments. Depending on the intended use, it is possible to use bothinorganic and organic pigments. Such additives are known to the personskilled in the art, examples being titanium dioxide pigments, e.g. ofthe rutile or anatase type, carbon black, zinc oxide, such as zincwhite, iron oxides, such as iron oxide yellow, iron oxide red, chromiumyellow, chromium green, nickel titanium yellow, ultramarine blue, cobaltblue, bismuth vanadate, cadmium yellow or cadmium red. Examples oforganic pigments are mono- or bisazo pigments, and metal complexesthereof, phthalocyanine pigments, polycyclic pigments, for exampleperylene, anthraquinone, thioindigo, quinacridone or triphenylmethanepigments, and diketopyrrolopyrrole, isoindolinone, e.g.tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone andquinophthalone pigments. The pigments can be used individually or elseas mixtures in the formulations. Depending on the intended use, thepigments are added to the formulations in amounts customary in the art,for example in an amount of from 0.1 to 60% by weight, 0.1 to 30% byweight or 10 to 30% by weight, based on the total composition.

The formulations can, for example, also comprise organic dyes from verydiverse classes. Examples are azo dyes, methine dyes, anthraquinone dyesor metal complex dyes. Customary concentrations are, for example, 0.1 to20%, in particular 1 to 5%, based on the total compositions.

The choice of additives depends on the field of application in questionand the properties desired for this field. The above-described additives(d) are customary in the art and are accordingly used in amountscustomary in the art.

The invention also provides compositions comprising, as components (a),at least one ethylenically unsaturated photopolymerizable compound whichis emulsified or dissolved in water.

Such radiation-curable aqueous prepolymer dispersions are availablecommercially in many variations. This is understood as meaning adispersion of water and at least one prepolymer dispersed therein. Theconcentration of the water in these systems is, for example, 2 to 80% byweight, in particular 30 to 60% by weight. The radiation-curableprepolymers or prepolymer mixture is present, for example, inconcentrations of from 95 to 20% by weight, in particular 70 to 40% byweight. In these compositions, the total of the percentages given forwater and prepolymers is in each case 100, the auxiliaries and additivesbeing added in varying amounts, depending on the intended use.

The radiation-curable film-forming prepolymers which are dispersed, andoften also dissolved, in water are mono- or polyfunctional ethylenicallyunsaturated prepolymers which can be initiated by free radicals and areknown per se for aqueous prepolymer dispersions, which have, forexample, a content of from 0.01 to 1.0 mol per 100 g of prepolymer ofpolymerizable double bonds, and also an average molecular weight of, forexample, at least 400, in particular from 500 to 10,000. However,depending on the intended use, prepolymers with higher molecular weightsare also suitable.

Polyesters containing polymerizable C—C double bonds and having an acidnumber of at most 10, polyethers containing polymerizable C—C doublebonds, hydroxyl-containing products of the reaction of a polyepoxidecontaining at least two epoxide groups per molecule with at least oneα,β-ethylenically unsaturated carboxylic acid, polyurethane(meth)acrylates, and acrylic copolymers containing α,β-ethylenicallyunsaturated acrylic radicals, as are described in EP 12339. Mixtures ofthese prepolymers can likewise be used. Also suitable are thepolymerizable prepolymers described in EP 33896, which are thioetheradducts of polymerizable prepolymers having an average molecular weightof at least 600, a carboxyl group content of from 0.2 to 15% and acontent of from 0.01 to 0.8 mol of polymerizable C—C double bonds per100 g of prepolymer. Other suitable aqueous dispersions based onspecific (meth)acrylic alkyl ester polymers are described in EP 41125,and suitable water-dispersible, radiation-curable prepolymers ofurethane acrylates can be found in DE 2936039.

As further additives, these radiation-curable aqueous prepolymerdispersions can also comprise the above-described additional additives(d), i.e., for example, dispersion auxiliaries, emulsifiers,antioxidants, light stabilizers, dyes, pigments, fillers, e.g. talc,gypsum, silica, rutile, carbon black, zinc oxide, iron oxides, reactionaccelerators, levelling agents, lubricants, wetting agents, thickeners,matting agents, antifoams and other auxiliaries customary in surfacecoating technology. Suitable dispersion auxiliaries are water-solublehigh molecular weight organic compounds having polar groups, for examplepolyvinyl alcohols, polyvinylpyrrolidone or cellulose ethers.Emulsifiers which may be used are nonionic, and, where appropriate, alsoionic, emulsifiers.

The photoinitiators of the formula II or III according to the inventioncan also be dispersed as such in aqueous solutions and added in thisdispersed form to the mixtures to be cured. Treated with suitablenonionic or, where appropriate, also ionic, emulsifiers, the compoundsof the formula II or III according to the invention can be incorporatedby mixing and e.g. binding into water. This produces stable emulsionswhich can be used as such as photoinitiators, in particular for aqueousphotocurable mixtures as described above.

In certain cases, it may be advantageous to use mixtures of two or moreof the photoinitiators according to the invention. It is of course alsopossible to use mixtures with known photoinitiators, e.g. mixtures withcamphorquinone, benzophenone, benzophenone derivatives, in particularalkyl-substituted benzophenones, acetophenone, acetophenone derivatives,for example α-hydroxycycloalkyl phenyl ketones or2-hydroxy-2-methyl-1-phenylpropanone, dialkoxyacetophenones, α-hydroxyor α-aminoacetophenones, for example4-methylthiobenzoyl-1-methyl-1-morpholinoethane,4-morpholinobenzoyl-1-benzyl-1-dimethylaminopropane,4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, forexample benzil dimethyl ketal, phenyl glyoxalates and derivativesthereof, dimeric phenyl glyoxalates, peresters, e.g.benzophenonetetracarboxylic peresters, as described, for example, in EP126541, monoacylphosphine oxides, for example(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bisacylphosphine oxides,for example bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpent-1-yl)phosphineoxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide orbis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide,trisacylphosphine oxides, halomethyltriazines, e.g.2-[2-(4-methoxyphenyl)vinyl]-4,6-bistrichloromethyl-[1,3,5]triazine,2-(4-methoxyphenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(3,4-dimethoxyphenyl)-4,6-bistrichloromethyl-[1,3,5]triazine,2-methyl-4,6-bistrichloromethyl-[1,3,5]triazine,hexaarylbisimidazole/coinitiator systems, e.g.ortho-chlorohexaphenylbisimidazole in combination with2-mercaptobenzothiazole; ferrocenium compounds or titanocenes, forexample dicyclopentadienylbis(2,6-difluoro-3-pyrrolophenyl)titantium.Coinitiators which may also be used are borate compounds.

In the case of the use of the photoinitiators according to the inventionin hybrid systems, in this connection mixtures of free-radically andcationically curing systems are thus intended, in addition to thefree-radical curing agents according to the invention, cationicphotoinitiators, for example benzoyl peroxide (other suitable peroxidesare described in U.S. Pat. No. 4,950,581, column 19, lines 17-25),aromatic sulfonium, phosphonium or iodonium salts, as described, forexample in U.S. Pat. No. 4,950,581, column 18, line 60 to column 19,line 10, or cyclopentadienylareneiron(II) complex salts, e.g.(η⁶-isopropylbenzene)(η⁵-cyclopentadienyl)iron(II) hexafluorophosphate,are used.

The invention also provides compositions in which the additionalphotoinitiators (c) are compounds of the formula VIII, IX, X, XI ormixtures thereof,

in which

R₂₅ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, —OCH₂CH₂—OR₂₉, morpholino,SCH₃, a group

or a group

n has a value from 2 to 10;

G₁ and G₂ independently of one another are end-groups of the polymericunit, in particular hydrogen or CH₃;

R₂₆ is hydroxyl, C₁-C₁₆alkoxy, morpholino, dimethylamino or—O(CH₂CH₂O)_(m)—C₁-C₁₆alkyl;

R₂₇ and R₂₈ independently of one another are hydrogen, C₁-C₆alkyl,phenyl, benzyl, C₁-C₁₆alkoxy or —O(CH₂CH₂O)_(m)—C₁-C₁₆alkyl, or R₂₇ andR28 together with the carbon atom to which they are bonded form acyclohexyl ring;

m is a number from 1-20;

where R₂₆, R₂₇ and R₂₈ are not all C₁-C₁₆alkoxy or—O(CH₂CH₂O)_(m)—C₁-C₁₆alkyl at the same time, and

R₂₉ is hydrogen,

R₃₀ and R₃₂ independently of one another are hydrogen or methyl;

R₃₁ is hydrogen, methyl or phenylthio, where the phenyl ring of thephenylthio radical is unsubstituted or substituted by C₁-C₄alkyl in the4-, 2-, 2,4- or 2,4,6-position;

R₃₃ and R₃₄ independently of one another are C₁-C₂₀alkyl, cyclohexyl,cyclopentyl, phenyl, naphthyl or biphenyl, where these radicals areunsubstituted or are substituted by halogen, C₁-C₁₂alkyl and/orC₁-C₁₂-alkoxy, or R₃₃ is an S- or N-containing 5- or 6-memberedheterocyclic ring, or are

R₃₅ is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl, theseradicals being unsubstituted or substituted by halogen, C₁-C₄alkyland/or C₁-C₄alkoxy, or R₃₅ is an S- or N-containing 5- or 6-memberedheterocyclic ring;

R₃₆ and R₃₇ independently of one another are unsubstitutedcyclopentadienyl or cyclopentadienyl substituted once, twice or threetimes by C₁-C₁₈alkyl, C₁-C₁₈alkoxy, cyclopentyl, cyclohexyl or halogen;and

R₃₈ and R₃₉ independently of one another are phenyl which is substitutedin at least one of the two ortho positions relative to thetitanium-carbon bond by fluorine atoms or CF₃, and which on the aromaticring may contain, as further substituents, unsubstituted pyrrolinyl orpyrrolinyl substituted by one or two C₁-C₁₂alkyl,di(C₁-C₁₂alkyl)aminomethyl, morpholinomethyl, C₂-C₄alkenyl,methoxymethyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl;

or polyoxaalkyl,

or R₃₈ and R₃₉

R₄₀, R₄₁ and R₄₂ independently of one another are hydrogen, halogen,C₂-C₁₂alkenyl, C₁-C₁₂alkoxy, C₂-C₁₂alkoxy interrupted by one to four Oatoms, cycylohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, unsubstitutedphenyl or phenyl substituted by C₁-C₄alkoxy, halogen, phenylthio orC₁-C₄-alkylthio; or biphenyl,

where R₄₀ and R₄₂ are not both hydrogen at the same time and in theradical

at least one radical R₄₀ or R₄₂ is C₁-C₁₂alkoxy, C₂-C₁₂alkoxyinterrupted by one to four O atoms, cyclohexyloxy, cyclopentyloxy,phenoxy or benzyloxy;

E₁ is O, S or NR₄₃; and

R₄₃ is C₁-C₈alkyl, phenyl or cyclohexyl.

R₂₅ as C₁-C₁₈alkyl can have the same meanings as described for thecompounds of the formulae I, II or III. Also, R₂₇ and R₂₈ as C₁-C₆alkyland R₂₆ as C₁-C₄alkyl can have the same meanings as described aboveapart from the respective number of carbon atoms.

C₁-C₁₈alkoxy is, for example, branched or unbranched alkoxy, for examplemethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy,2,4,4-trimethylpent-1-yloxy, 2-ethylhexyloxy, nonyloxy, decyloxy,dodecyloxy or octadecyloxy.

C₂-C₁₂alkoxy has the meanings given above apart from the correspondingnumber of carbon atoms.

C₁-C₁₆alkoxy has the same meanings as described above apart from thecorresponding number of carbon atoms, and decyloxy, methoxy and ethoxyare preferred, in particular methoxy and ethoxy.

The radical —O(CH₂CH₂O)_(m)—C₁-C₁₆alkyl stands for 1 to 20 consecutiveethylene oxide units whose chain ends with a C₁-C₁₆alkyl. Preferably, mis 1 to 10, e.g. 1 to 8, in particular 1 to 6. Preferably, the ethyleneoxide unit chain is terminated with a C₁-C₁₀alkyl, e.g. C₁-C₈alkyl, inparticular with a C₁-C₄alkyl.

R₃₁ as a substituted phenylthio ring is, preferably, p-tolylthio.

R₃₃ and R₃₄ as C₁-C₂₀alkyl are linear or branched and are, for example,C₁-C₁₂alkyl, C₁-C₈alkyl, C₁-C₆alkyl or C₁-C₄alkyl. Examples are methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl,nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl or icosyl. Preferably, R₃₃ as alkyl isC₁-C₈alkyl.

R₃₃, R₃₄ and R₃₅ as substituted phenyl are mono- to pentasubstituted,e.g. mono-, di- or trisubstituted, in particular tri- or disubstituted,on the phenyl ring. Substituted phenyl, naphthyl or biphenyl aresubstituted e.g. with a linear or branched C₁-C₄alkyl such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl orwith a linear or branched C₁-C₄alkoxy such as methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy or t-butoxy,preferably with methyl or methoxy.

If R₃₃, R₃₄ and R₃₅ are an S- or N-containing 5- or 6-memberedheterocyclic ring, they are, for example, thienyl, pyrrolyl or pyridyl.

In the expression di(C₁-C₁₂alkyl)aminomethyl, C₁-C₁₂alkyl has the samemeanings as given above.

C₂-C₁₂alkenyl is linear or branched, can be mono- or polyunsaturated andis, for example, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl,2-butenyl, 1,3-pentadienyl, 1-hexenyl or 1-octenyl, in particular allyl.

C₁-C₄alkylthio is linear or branched and is, for example, methylthio,ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio,s-butylthio or t-butylthio, preferably methylthio.

C₂-C₄alkenyl is, for example, allyl, methallyl, 1-butenyl or 2-butenyl.

Halogen is fluorine, chlorine, bromine and iodine, preferably, fluorine,chlorine and bromine.

The term polyoxaalkyl includes C₂-C₂₀alkyl interrupted by 1 to 9 O atomsand stands, for example, for structural units such as CH₃—O—CH₂—,CH₃CH₂—O—CH₂CH₂—, CH₃O[CH₂CH₂O]_(y)—, where y=1-9, —(CH₂CH₂O)₇CH₂CH₃,—CH₂—CH(CH₃)—O—CH₂—CH₂CH₃.

Preference is given to compositions in which

R₂₅ is hydrogen, —OCH₂CH₂—OR₂₉, morpholino, SCH₃, a group

or a group

R₂₆ is hydroxyl, C₁-C₁₆alkoxy, morpholino or dimethylamino;

R₂₇ and R₂₈ independently of one another are C₁-C₄alkyl, phenyl, benzylor C₁-C₁₆alkoxy, or

R₂₇ and R₂₈ together with the carbon atom to which they are bonded forma cyclohexyl ring;

R₂₉ is hydrogen or

R₃₀, R₃₁ and R₃₂ are hydrogen;

R₃₃ is C₁-C₁₂alkyl, unsubstituted phenyl or phenyl substituted byC₁-C₁₂alkyl and/or C₁-C₁₂alkoxy;

R₃₄ is

and

R₃₅ is phenyl which is substituted by C₁-C₄alkyl and/or C₁-C₄alkoxy.

Preferred compounds of the formulae VIII, IX, X and XI areα-hydroxycyclohexyl phenyl ketone or2-hydroxy-2-methyl-1-phenylpropanone,(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, benzil dimethylketal, (2,4,6-trimethylbenzoyl)phenylphosphine oxide,bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide orbis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide anddicyclopentadienylbis(2,6-difluoro-3-pyrrolo)titanium.

Preference is also given to compositions in which, in the formula VIIIR₂₇ and R₂₈ independently of one another are C₁-C₆alkyl, or togetherwith the carbon atom to which they are bonded form a cyclohexyl ring,and R₂₆ is hydroxyl.

The proportion of compounds of the formula II and/or III (photoinitiatorcomponent (b)) in the mixture with compounds of the formulae VIII, IX, Xand/or XI (=photoinitiator component (c)) is 5 to 99%, e.g. 20-80%,preferably 25 to 75%.

Also important are compositions in which, in the compounds of theformula VIII, R₂₇ and R₂₈ are identical and are methyl, and R₂₆ ishydroxyl or isopropoxy.

Likewise preferred are compositions comprising compounds of the formulaII and/or III and compounds of the formula X in which

R₃₃ is unsubstituted or mono- to tri- C₁-C₁₂alkyl- and/orC₁-C₁₂alkoxy-substituted phenyl or C₁-C₁₂alkyl;

R₃₄ is the group

or phenyl; and

R₃₅ is phenyl substituted by one to three C₁-C₄alkyl or C₁-C₄alkoxy.

Of particular interest are compositions as described above whichcomprise photoinitiator mixtures of the formulae II, III, VIII, IX, Xand/or XI and are liquid at room temperature.

The preparation of the compounds of the formulae VIII, IX, X and XI isgenerally known to the person skilled in the art and some of thecompounds are available commercially. The preparation of oligomericcompounds of the formula VIII is described, for example, in EP 161463. Adescription of the preparation of compounds of the formula IX can, forexample, be found in EP 209831. The preparation of compounds of theformula X is disclosed, for example, in EP 7508, EP 184095 and GB2259704. The preparation of compounds of the formula XI is described,for example, in EP 318894, EP 318893 and EP 565488.

The photopolymerizable compositions advantageously comprise thephotoinitiator in an amount of from 0.05 to 20% by weight, e.g. 0.05 to15% by weight, preferably 0.1 to 5% by weight, based on the composition.The amount of photoinitiator stated is based on the total of all addedphotoinitiators if mixtures thereof are used, i.e. both on thephotoinitiator (b) and on the photoinitiators (b)+(c).

Compounds according to the invention in which Z₁ or Z₂ aresiloxane-containing radicals are particularly suitable asphotoinitiators for surface coatings, in particular vehicle paints.These photoinitiators are not distributed as homogeneously as possiblein the formulation to be cured, but enriched in a targeted manner on thesurface of the coating to be cured, i.e. a targeted orientation of theinitiator to the surface of the formulation takes place.

The photopolymerizable compositions can be used for various purposes,for example as printing inks, such as screen printing inks, flexographicprinting inks or offset printing inks, as clearcoats, as colour coats,as white coats, e.g. for wood or metal, as powder coatings, as paints,inter alia for paper, water, metal or plastic, as daylight-curablecoatings for marking buildings and roads, for photographic reproductionprocesses, for holographic recording materials, for image recordingprocesses or for the production of printing plates which can bedeveloped using, for example, organic solvents or aqueous-alkalinemedia, for the production of masks for screen printing, as dentalfilling materials, as adhesives, as pressure-sensitive adhesives, aslaminating resins, as photoresists, e.g. galvanoresists, etch orpermanent resists, both liquid and dry films, as photostructurabledielectrics, and as solder stopping masks for electronic circuits, asresists for the preparation of colour filters for any type of screen orfor producing structures in the production process of plasma displaysand electroluminescence displays, for the production of opticalswitches, optical gratings (interference gratings), for the preparationof three-dimensional objects by mass curing (UV curing in transparentmoulds) or by the stereolithography process, as is described, forexample, in U.S. Pat. No. 4,575,330, for the preparation of compositematerials (e.g. styrenic polyesters which may contain glass fibresand/or other fibres and other auxiliaries) and other thick-layermaterials, for the preparation of gel coats, for the coating or sealingof electronic components or as coatings for optical fibres. Thecompositions are also suitable for the preparation of optical lenses,e.g. contact lenses and Fresnel lenses, and for the preparation ofmedical instruments, auxiliaries or implants.

The compositions are also suitable for the preparation of gels havingthermotropic properties. Such gels are described, for example, in DE19700064 and EP 678534.

Furthermore, the compositions can be used in dry-film paints, as aredescribed, for example, in Paint & Coatings Industry, April 1997, 72 orPlastics World, Volume 54, No. 7, page 48(5).

The compounds according to the invention can also be used as initiatorsfor emulsion, bead or suspension polymerizations or as initiators of apolymerization for the fixing of ordered states of liquid-crystallinemono- and oligomers, or as initiators for the fixing of dyes to organicmaterials.

In surface coatings, mixtures of a prepolymer with polyunsaturatedmonomers are often used which also contain a monounsaturated monomer.The prepolymer here is primarily responsible for the properties of thecoating film, and variation thereof allows the person skilled in the artto influence the properties of the cured film. The polyunsaturatedmonomer functions as a crosslinking agent which renders the coating filminsoluble. The monounsaturated monomer functions as a reactive diluent,by means of which the viscosity is reduced without the need to use asolvent.

Unsaturated polyester resins are mostly used in two-component systemstogether with a monounsaturated monomer, preferably with styrene. Forphotoresists, specific one-component systems are often used, for examplepolymaleimides, polychalcones or polyimides, as are described in DE2308830.

The compounds according to the invention and mixtures thereof may alsobe used as free-radical photoinitiators or photoinitiating systems forradiation-curable powder coatings. The powder coatings may be based onsolid resins and monomers containing reactive double bonds, for examplemaleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. Afree-radically UV-curable powder coating can be formulated by mixingunsaturated polyester resins with solid acrylamides (e.g. methylmethacrylamide glycolate) and with a free-radical photoinitiatoraccording to the invention, as described, for example, in the paper“Radiation Curing of Powder Coating”, Conference Proceedings, RadtechEurope 1993 by M. Wittig and Th. Gohmann. Similarly, free-radicallyUV-curable powder coatings can be formulated by mixing unsaturatedpolyester resins with solid acrylates, methacrylates or vinyl ethers andwith a photoinitiator (or photoinitiator mixture) according to theinvention. The powder coatings can also comprise binders, as described,for example, in DE 4228514 and EP 636669. The UV-curable powder coatingscan also comprise white or coloured pigments. Thus, for example,preferably rutile titanium dioxide may be used in concentrations of upto 50% by weight in order to obtain a cured powder coating with goodcoverage. The process normally involves electrostatic or tribostaticspraying of the powder onto the substrate, for example metal or wood,melting the powder by heating and, after a smooth film has formed,radiation-curing of the coating with ultraviolet and/or visible light,e.g. using medium-pressure mercury lamps, metal halide lamps or xenonlamps. A particular advantage of the radiation-curable powder coatingscompared with their thermally curable counterparts is that the flow timeafter the melting of the powder particles can be extended as desired inorder to ensure the formation of a smooth, high-gloss coating. Incontrast to thermally curable systems, radiation-curable powder coatingscan be formulated without the desired effect of a reduction in theirservice life such that they melt at relatively low temperatures. Forthis reason, they are also suitable as coatings for heat-sensitivesubstrates, for example wood or plastics.

In addition to the photoinitiators according to the invention, thepowder coating formulations can also comprise UV absorbers. Appropriateexamples have been listed above under points 1-8.

The photocurable compositions according to the invention are suitable,for example, as coating substances for substrates of all kinds, e.g.wood, textiles, paper, ceramic, glass, plastics such as polyesters,polyethylene terephthalate, polyolefins or cellulose acetate, inparticular in the form of films, and also metals such as Al, Cu, Ni, Fe,Zn, Mg or Co and GaAs, Si or SiO₂, on which a protective coating or, forexample by imagewise exposure, an image is to be applied.

The substrates can be coated by applying a liquid composition, asolution or suspension to the substrate. The choice of solvent and theconcentration depend primarily on the type of composition and on thecoating procedure. The solvent should be inert, i.e. it should notundergo any chemical reaction with the components and should be capableof being removed again after the coating operation, in the dryingprocess. Examples of suitable solvents are ketones, ethers and esters,such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone,cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran,2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol,1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl3-ethoxypropionate.

Using known coating processes, the formulation is applied to asubstrate, e.g. by spincoating, dip coating, knife coating, curtaincoating, brushing, spraying, especially, for example, by electrostaticspraying and reverse-roll coating, and by electrophoretic deposition. Itis also possible to apply the photosensitive layer to a temporary,flexible support and then to coat the final substrate, e.g. acopper-laminated circuit board, by means of layer transfer vialamination.

The amount applied (layer thickness) and the type of substrate (layersupport) are dependant on the desired field of application. The suitablelayer thicknesses for the respective fields of application, e.g. in thephotoresist field, printing ink field or paint field are known to theperson skilled in the art. Depending on the field of application, thelayer thickness range generally includes values from about 0.1 μm tomore than 10 mm.

The radiation-sensitive compositions according to the invention areused, for example, as negative resists which have very highphotosensitivity and can be developed in an aqueous-alkaline mediumwithout swelling. They are suitable as photoresists for electronics,such as galvanoresists, etch resists, both in liquid and also dry films,solder stopping resists, as resists for the production of colour filtersfor any desired type of screen, or for the formation of structures inthe manufacturing process of plasma displays and electroluminescencedisplays, for the production of printing plates, for example offsetprinting plates, for the production of printing formes for typographicprinting, planographic printing, intaglio printing, flexographicprinting or screen printing formes, the production of relief copies,e.g. for the production of texts in Braille, for the production ofstamps, for use in moulding etching or use as microresists in theproduction of integrated circuits. The compositions may also be used asphotostructurable dielectrics, for the encapsulation of materials or asinsulator coating for the production of computer chips, printed circuitsand other electrical or electronic components. The possible layersupports and the processing conditions of the coated substrates arevaried accordingly.

The compounds according to the invention are also used for theproduction of single-layer or multilayer materials for image recordingor image duplication (copies, reprography), which may be monotone ormulticoloured. Furthermore, these materials can also be used as colourtesting systems. In this technology, it is also possible to useformulations which contain microcapsules and, to generate the image, athermal step can be connected downstream of the exposure step. Suchsystems and technologies and their applications are described, forexample, in U.S. Pat. No. 5,376,459.

For photographic information recording, films made of polyester,cellulose acetate or plastic-coated papers, for example, are used, andfor offset printing formes, specially treated aluminium, for example, isused, for the production of printed circuits, copper-faced laminates,for example, are used, and for the production of integrated circuits,silicon wafers are used. The usual layer thicknesses for photographicmaterials and offset printing forms are generally about 0.5 μm to 10 μm,and for printed circuits are from 1.0 μm to about 100 μm.

After the substrates have been coated, the solvent is usually removed bydrying, to leave a layer of the photoresist on the support. The term“imagewise” exposure encompasses both exposure via a photomaskcontaining a predetermined pattern, for example a diapositive, exposureby a laser beam which is moved, for example under control by a computer,over the surface of the coated substrate, thereby generating an image,and irradiation with computer-controlled electron beams. It is alsopossible to use masks of liquid crystals which can be controlled pixelby pixel in order to generate digital images, as described, for example,by A. Bertsch, J. Y. Jezequel, J. C. Andre in Journal of Photochemistryand Photobiology A: Chemistry 1997, 107, p. 275-281 and by K.-P. Nicolayin Offset Printing 1997, 6, p. 34-37.

Conjugated polymers, for example polyanilines, can be converted from asemiconducting state to a conducting state by doping with protons. Thephotoinitiators according to the invention can also be used for theimagewise exposure of polymerizable compositions which contain suchpolymers in order to form conducting structures (in the irradiatedzones) which are embedded in the insulating material (unexposed zones).Such materials can, for example, be used as wiring or connectingcomponents for the production of electrical or electronic components.

Following the imagewise exposure of the material and prior to thedeveloping, it may be advantageous to carry out a thermal treatment fora relatively short period. Here, only the exposed parts are thermallycured. The temperatures used are generally 50-150° C., preferably80-130° C.; the thermal treatment time is usually between 0.25 and 10minutes.

Furthermore, the photocurable composition can be used in a process forthe production of printing formes or photoresists, as described, forexample, in DE 4013358. Herein, prior to, simultaneously with orfollowing the imagewise irradiation, the composition is briefly exposedto visible light having a wavelength of at least 400 nm without a mask.Following the exposure and the optional thermal treatment, the unexposedareas of the photoresist are removed using a developer in a manner knownper se.

As already mentioned, the compositions according to the invention can bedeveloped by aqueous-alkaline media. Suitable aqueous-alkaline developersolutions are, in particular, aqueous solutions of tetraalkylammoniumhydroxides or of alkali metal silicates, phosphates, hydroxides andcarbonates. Relatively small amounts of wetting agents and/or organicsolvents can also be added to these solutions. Typical organic solventswhich may be added to the developer liquids in small amounts are, forexample, cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixturesof such solutions.

Photocuring is of great importance for printing inks since the dryingtime of the binder is a crucial factor for the production rate ofgraphic products and should be in the order of magnitude of fractions ofseconds. UV-curable inks are of importance particularly for screen,flexographic and offset printing.

As already mentioned, the mixtures according to the invention are alsohighly suitable for the production of printing plates. Here, mixtures ofsoluble linear polyamides or styrene/butadiene or styrene/isoprenerubber, polyacrylates or polymethyl methacrylates containing carboxylgroups, polyvinyl alcohols or urethane acrylates with photopolymerizablemonomers, for example acryl- or methacrylamides or acrylic ormethacrylic esters, and a photoinitiator, for example, are used. Filmsand plates made from these systems (wet or dry) are exposed via thenegative (or positive) of the print original, and the uncured parts aresubsequently washed out using a suitable solvent.

A further field of use for photocuring is the coating of metals, forexample the coating of metal sheets and tubes, cans or bottlecaps, andthe photocuring of plastic coatings, for example PVC-based floor or wallcoverings. Examples of the photocuring of paper coatings are thecolourless coating of labels, record sleeves or book covers.

Likewise of interest is the use of the compounds according to theinvention for the curing of mouldings made from composite materials. Thecomposite material consists of a self-supporting matrix material, e.g. aglass-fibre fabric, or else, for example, plant fibres [cf. K.-P. Mieck,T. Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnatedwith the photocuring formulation. Mouldings made of composite materialsproduced using the compounds according to the invention have highmechanical stability and resistance. The compounds according to theinvention can also be used as photocuring agents in moulding,impregnation or coating materials, as described, for example, in EP7086. Such materials are, for example, fine coating resins, which aresubject to strict requirements with regard to their curing activity andyellowing resistance, fibre-reinforced mouldings, for example planar orlongitudinally or transversely corrugated light-diffusing panels.Processes for the production of such mouldings, for example hand lay-uptechniques, fibre lay-up spraying, centrifugal or winding techniques,are described, for example, by P. H. Selden in “GlasfaserverstärkteKunststoffe” [Glass-fibre-reinforced plastics], page 610, SpringerVerlag Berlin-Heidelberg-New York 1967. Examples of articles which maybe produced by this method are boats, chipboard or plywood panels coatedon both sides with glass-fibre-reinforced plastic, pipes, sportarticles, roof coverings, and containers etc. Further examples ofmoulding, impregnation and coating materials are UP resin fine coatingsfor mouldings containing glass fibres (GFP), e.g. corrugated sheets andpaper laminates. Paper laminates may be based on urea or melamineresins. The fine coating is produced on a support (e.g. a film) prior tothe production of the laminate. The photocurable compositions accordingto the invention can also be used for casting resins or for embeddingarticles, e.g. electronic components etc. Moreover, they can also beused for the lining of cavities and pipes. For curing, medium-pressuremercury lamps are used, as are customary in UV curing. However, lessintensive lamps are also of particular interest, e.g. those of the typeTL 40W/03 or TL40W/05. The intensity of these lamps correspondsapproximately to that of sunlight. It is also possible to use directsunlight for the curing. It is a further advantage that the compositematerial can be removed from the light source in a partially cured,plastic state and can be deformed. Curing is then carried out tocompletion.

The compositions and compounds according to the invention can also beused for the preparation of optical waveguides and optical switches, usebeing made of the generation of a difference in the refractive indexbetween exposed and unexposed areas.

Also important is the use of photocurable compositions for imagingprocesses and for the optical production of information carriers. Here,as already described above, the coat (wet or dry) applied to the supportis irradiated with UV or visible light via a photomask and the unexposedareas of the coat are removed by treatment with a solvent (=developer).The photocurable layer can also be applied to the metal by anelectrodeposition technique. The exposed areas are crosslinked/polymericand thus insoluble and remain on the support. Appropriate colorationproduces visible images. If the support is a metallicized layer, thenthe metal can be removed from the unexposed areas by etching afterexposure and developing, or can be strengthened by electroplating.Printed electronic circuits and photoresists can be produced in thisway.

The photosensitivity of the compositions according to the inventiongenerally ranges from about 200 nm to about 600 nm (UV range). Suitableradiation comprises, for example, sunlight or light from artificiallight sources. Therefore, a large number of very different types oflight sources can be used. Point sources and flat radiators (lampcarpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps,medium-pressure, high-pressure and low-pressure mercury lamps,optionally doped with metal halides (metal halogen lamps),microwave-stimulated metal vapour lamps, excimer lamps, superactinicfluorescent tubes, fluorescent lamps, incandescent argon lamps,flashlights, photographic floodlight lamps, light-emitting diodes (LED),electron beams and X-rays. The distance between the lamp and thesubstrate to be exposed according to the invention can vary depending onthe intended use and lamp type and intensity, e.g. between 2 cm and 150cm. Of particular suitability are laser light sources, e.g. excimerlasers, such as krypton F lasers for exposure at 248 nm. It is alsopossible to use lasers in the visible region. Using this method it ispossible to produce printed circuits in the electronics industry,lithographic offset printing plates or relief printing plates, and alsophotographic image recording materials.

The invention therefore also provides a process for thephotopolymerization of nonvolatile monomeric, oligomeric or polymericcompounds having at least one ethylenically unsaturated double bond,which comprises irradiating a composition as described above with lightin the range from 200 to 600 nm. The invention also provides for the useof the compounds of the formula II or III as photoinitiators for thephotopolymerization of nonvolatile monomeric, oligomeric or polymericcompounds having at least one ethylenically unsaturated double bond byirradiation with light in the range from 200 to 600 nm.

The invention also provides for the use of the above-describedcomposition or a process for the preparation of pigmented andunpigmented surface coatings, printing inks, for example screen printinginks, offset printing inks, flexographic printing inks, powder coatings,printing plates, adhesives, dental compositions, optical waveguides,optical switches, colour testing systems, composite materials, gelcoats, glass fibre cable coatings, screen printing stencils, resistmaterials, colour filters, use for the encapsulation of electrical andelectronic components, for the production of magnetic recordingmaterials, for the production of three-dimensional objects usingstereolithography, for photographic reproductions, and for use as imagerecording material, in particular for holographic recordings, fordecolouring materials, for decolouring materials for image recordingmaterials, for image recording materials using microcapsules.

The invention likewise provides a coated substrate which has been coatedon at least one surface with a composition as described above, and alsoa process for the photographic production of relief images in which acoated substrate is subjected to imagewise exposure and then theunexposed portions are removed with a solvent. The imagewise exposurecan be carried out via a mask or by means of a laser beam. Of particularinterest here is exposure by means of a laser beam.

The examples below illustrate the invention in more detail, although itis not intended that the invention be limited to the examples. Unlessstated otherwise, parts and percentages are based, as elsewhere in thedescription and in the claims, on the weight. Wherever reference is madeto alkyl or alkoxy radicals having more than three carbon atoms withoutstating the isomer, then the n-isomers are always intended.

EXAMPLE 1 Preparation of lithium(2,4,6-trimethylbenzoyl)isobutylphosphine

34.4 ml (0.055 mol, +10%) of butyllithium 1.6M are slowly addeddropwise, at 0° C.-10° C., to 4.5 g (0.025 mol) of isobutylphosphine(50% solution in toluene) in 30 ml of tetrahydrofuran. At the sametemperature, 4.6 g (0.025 mol) of 2,4,6-trimethylbenzoyl chloride arethen added dropwise. After warming to room temperature, the titlecompound is obtained as an orange suspension. The shift signal δ in the³¹P-NMR spectrum appears at 50 ppm, measured against CDCl₃ as reference.

EXAMPLE 2 Preparation of lithium(2,4,6-trimethylbenzoyl)(2,4,4-trimethylpentyl)phosphine

The compound is obtained analogously to the process described in example1 using 2,4,6-trimethylbenzoyl chloride and2,4,4-trimethylpentylphosphine as starting materials. The shift signal δin the ³¹P-NMR spectrum appears at 49.2 ppm, measured against CDCl₃ asreference.

EXAMPLE 3 Preparation of 2,4,6-trimethylbenzoylisobutylphosphine

The suspension obtained as described in example 1 is added dropwise to amixture of toluene/water and acetic acid. The organic phase is separatedoff, dried over magnesium sulfate and evaporated on a rotary evaporator(Rotavap) under argon. The residue is distilled using bulb-tube ovendistillation at 110° C. and 0.1 torr. 6 g of the title compound areobtained as a pale yellow oil. The shift signal δ [ppm] in the ³¹P-NMRspectrum appears at −37.5.

Shift signals δ [ppm] in the ¹H-NMR spectrum: 1.01 (dd); 1.85 (m); 1.98(m); 2.23 (s); 2.28 (s); 3.91 (t); 4.66 (t; 1H on the P) 6.82 (s);(measured in C₆D₆).

EXAMPLE 4 Preparation of 2,4,6-trimethylbenzoylisobutylbenzylphospineoxide

4.30 g (0.025 mol) of benzyl bromide are slowly added dropwise at roomtemperature to the suspension obtained as described in example 1. Afterstirring for 1 hour at room temperature, the orange reaction suspensionis evaporated on a Rotavap. The residue is taken up in 50 ml of tolueneand treated with 4.2 g (0.0375 mol) of hydrogen peroxide 30%. Afterstirring for 2 hours at 20-30° C., the reaction is complete. Thereaction emulsion is poured onto water and washed with aqueous saturatedsodium hydrogencarbonate solution, then dried over magnesium sulfate andfiltered. The filtrate is evaporated on a Rotavap. The residue ispurified over silica gel and dried in a high vacuum. 6.0 g of the titlecompound are obtained as a yellow viscous oil.

The shift signal δ in the ³¹P-NMR spectrum appears at 39.6 ppm, measuredagainst CDCl₃ as reference.

The corresponding signals in the ¹H-NMR spectrum (ppm), measured inCDCl₃, are: 7.1-7.2 (m), 6.7 (s), 3.1-3.4 (m), 2.15 (s), 2.0 (s),1.6-1.9 (m) and 0.87-0.93 (q).

EXAMPLES 5-14 Were Prepared Analogously

The compounds of examples 5-14 are obtained analogously to the methoddescribed in example 4 using the corresponding starting materials. Thestructures and analytical data are given in table 1.

TABLE 1

NMR data Ex. R₆ Z₁ Starting materials δ in [ppm] 5 2,4,4-trimethyl-benzyl lithium (2,4,6-tri- ³¹P: 39.25 pentyl methylbenzoyl)- ¹H:0.97-0.85 (d); 2,4,4-trimethyl- 1.01-1.05 (q); 1.19- pentylphospine/1.24 (t); 1.42-1.97 benzyl bromide (m); 1.97 (s); 1.99- 2.22 (m);3.19-3.50 (m), 4.03-5.53 (q); 6.78 (s); 7.14-7.36 (m) 6 2,4,4-trimethyl-allyl lithium (2,4,6-tri- ³¹P: 39.06 pentyl methylbenzoyl)- ¹H: 1.11(d);1.13- 2,4,4-trimethyl- 1.70 (t); 1.76-1.39 pentylphospine/ (m);1.72-2.14 (m); allyl bromide 2.28-2.31 (d); 2.76-2.88 (m); 5.20-5.27(m); 5.77-5.90 (m); 6.86 (s) 7 2,4,4-trimethyl- isobutyl lithium(2,4,6-tri- ³¹P: 42.0 pentyl methylbenzoyl)- ¹H: 0.95 (d); 1.07-2,4,4-trimethyl- 1.37 (m); 1.72-2.15 pentylphospine/ (m); 2.28 (s); 2.33isobutyl bromide (s); 6.86 (s) 8 2,4,4-trimethyl- 2-ethylhexyl lithium(2,4,6-tri- ³¹P: 40.77 pentyl methylbenzoyl)- ¹H: 0.92-0.95 (m);2,4,4-trimethyl- 1.19-1.28 (m); pentylphospine/ 1.46-1.59 (m);2-ethylhexyl bro- 1.73-2.28 (m); 2.46 mide (s); 6.69 (s) 9 isobutyln-butyl lithium (2,4,6-tri- ³¹P: 42.5 methylbenzoyl)- ¹H: 1.03 (d); 1.08isobutylphospine/ (d); 1.55-1.80 (m); n-butyl bromide 2.25 (m); 2.28(s); 2.31 (s); 6.86 (s) 10 isobutyl allyl lithium (2,4,6-tri- ³¹P: 39.2methylbenzoyl)- ¹H: 1.04 (d); 1.07 isobutylphospine/ (d); 1.83 (m); 2.19allyl bromide (m); 2.28 (s); 2.31 (s); 2.84 (m); 5.21 (m); 5.27 (d);5.83 (m); 6.86 (s) 11 isobutyl —CH₂(CO)OCH₃ lithium (2,4,6-tri- ³¹P:36.0 methylbenzoyl)- ¹H: 1.07 (d); 1.09 isobutylphospine/ (d); 2.02 (m);2.22 methyl bromate (m); 2.29 (s); 2.34 (s); 3.21 (m); 3.72 (s); 6.88(s) 12 isobutyl —CH₂Si(CH₃)₂Si(CH₃)₃ lithium (2,4,6-tri- ³¹P: 41.9methylbenzoyl)- ¹H: 0.10 (s); 0.22 isobutylphospine/ (s); 0.32 (s); 1.02chloromethylpenta- (d); 1.07 (d); 1.20- methyldisiloxane 1.42 (m); 1.86(m); 1.96-2.04 (m); 2.28 (s); 2.31 (s); 6.86 (s) 13 isobutyl2-ethylhexyl lithium (2,4,6-tri- ³¹P: 42.8 methylbenzoyl)- ¹H: 0.87 (m);1.06 isobutylphospine/ (d); 1.09 (d); 1.26 2-ethylhexyl bro- (m); 1.45(m); 1.74 mide (m); 1.90 (m); 2.17 (m); 2.28 (s); 2.33 (s); 6.86 (s) 14isobutyl —CH(CH₃)(CO)OC₈H₁₇ lithium (2,4,6-tri- ³¹P: 34.9methylbenzoyl)- ¹H: 0.81-0.88 (m); isobutylphospine/ 1.07 (dd); 1.15-octyl 2-bromo- 1.34 (m); 1.40 (d); propionate isomer 1.49 (m); 1.75 (m);mixture 2.05-2.40 (m); 2.26 (s); 2.28 (s); 2.29 (s); 2.33 (s); 3.63 (m);4.01 (m); 6.85 (s)

EXAMPLE 15 Preparation of2,4,6-trimethylbenzoylisobutyl-(2-hydroxycyclohexyl)phosphine oxide

2.30 g (0.02 mol) of cyclohexene oxide are slowly added dropwise at roomtemperature to a suspension prepared as described in example 1. Afterheating to 50-55° C. and stirring for 1 hour at this temperature, thereaction mixture is treated with acetic acid and evaporated on aRotavap. The residue is taken up in 50 ml of toluene and treated with3.4 g (0.03 mol) of hydrogen peroxide (30%). After stirring for 2 hoursbetween 20-30° C. the reaction is complete. The reaction emulsion ispoured onto water and washed with aqueous saturated sodiumhydrogencarbonate solution, then dried over magnesium sulfate andfiltered. The filtrate is evaporated on a Rotavap. The residue ispurified over silica gel and dried under a high vacuum. The titlecompound is obtained as a white solid.

The shift signal δ [ppm] in the ³¹P-NMR spectrum appears at 48.0. Shiftsignals δ [ppm] in the ¹H-NMR spectrum: 1.08 (d); 1.09 (d); 1.28 (m);1.42 (m); 1.78-1.94 (m); 2.16 (m); 2.29 (s); 2.34 (s); 3.93 (m); 6.88(s); (measured in CDCl₃).

EXAMPLES 16-17

The compounds of examples 16 and 17 are prepared analogously to themethod described in example 15 using the corresponding startingmaterial. The structures and analytical data are shown in table 2.

TABLE 2

NMR data Ex. R₆ Z₁ Starting materials δ in [ppm] 16 isobutyl

lithium (2,4,6-tri- methylbenzoyl)- isobutylphospine/ styrene oxide ³¹P:43.8 ¹H: 1.08 (d); 1.82 (m); 2.18 (m); 2.27 (m); 2.32 (s); 2.36 (s);4.55 (s); 5.11 (dd); 6.92(s); 7.29-7.37 (m) (main component - twodiastereomers) 17 isobutyl

lithium (2,4,6-tri- methylbenzoyl)- isobutylphosphine/ chlorobenzal-dehyde ³¹P: 37.7; 38.3 ¹H: 0.82 (d); 0.87 (d); 1.71-1.85 (m); 2.22 (s);2.29 (s); 5.33 (d); 6.85 (s); 7.32 (d); 7.41 (d) (contains seconddiastereomers)

EXAMPLE 18 Preparation of2,4,6-trimethylbenzoyl-(2,6-dimethoxybenzoyl)isobutylphosphine oxide

5.30 g (0.026 mol) of 2,6-dimethoxybenzoyl chloride are slowly addeddropwise at room temperature to a suspension as described in example 1.After the mixture has been stirred for 1 hour at room temperature, theorange reaction suspension is concentrated on a Rotavap. The residue istaken up in 50 ml of toluene and treated with 3.4 g (0.03 mol) ofhydrogen peroxide (30%). After stirring for 2 hours between 20-30° C.,the reaction is complete. The reaction emulsion is poured onto water andwashed with aqueous saturated sodium hydrogencarbonate solution, thendried over magnesium sulfate and filtered. The filtrate is evaporated ona Rotavap. The residue is purified over silica gel and dried under anhigh vacuum. 3.8 g of the title compound are obtained as a slightlyyellow solid having an m.p. of 105-106° C.

The shift signal δ [ppm] in the ³¹P-NMR spectrum appears at 27.7. Shiftsignals δ [ppm] in the ¹H-NMR spectrum: 1.05 (dd); 2.12-2.37 (m); 2.26(2s); 3.56 (s); 6.54 (d); 6.85; 7.35 (t); (measured in CDCl₃).

EXAMPLES 19-21

The compounds of examples 19-21 are prepared analogously to the methoddescribed in example 18 using the corresponding starting materials. Thestructures and analytical data are given in table 3.

TABLE 3

NMR data Ex. R₆ Y₁ Starting materials δ in [ppm] 19 2,4,4-trimethyl-2,6-dimethoxyphenyl lithium (2,4,6-tri- ³¹P: 27.6 pentyl methylbenzoyl)-¹H: 0.7 (d); 0.87- 2,4,4-trimethyl- 1.22 (m); 1.83-2.43 pentylphospine/(m); 3.34 (s); 6.32 2,6-dimethoxy- (d); 6.66 (s); 7.16 benzoyl chloride(t) 20 isobutyl ethoxy lithium (2,4,6-tri- ³¹P: 24.1 methylbenzoyl)-iso-¹H: 1.07 (d); 1.11 butylphospine/ (d); 1.29 (t); 2.15- ethylchloroformate 2.27 (m); 2.29 (s); 2.31 (s); 4.32 (m); 6.88 (s) 21isobutyl diethylamino lithium (2,4,6-tri- ³¹P: 29.5 methylbenzoyl)-iso-¹H: 1.02 (d); 1.03 butylphospine/ (t); 1.09 (d); 1.15 diethylcarbamoyl(t); 2.10-2.33 (m); chloride 2.28 (s); 2.29 (s); 3.35 (m); 3.93 (m);6.85 (s)

EXAMPLE 22

A UV-curable white coat is prepared by mixing

67.5 parts of polyester acrylate oligomer (^(RTM)EBECRYL 830, UCB,Belgium)

5.0 parts of hexanediol diacrylate

2.5 parts of trimethylolpropane triacrylate

25.0 parts of rutile titanium dioxide (^(RTM)R-TC2, Tioxide, France)

2.0 parts of the photoinitiator from example 19

The coating is applied to a coil-coated aluminium sheet using a 100 μmslotted doctor knife and then cured. Curing is carried out by conveyingthe sample twice, on a conveyor belt which is moving at a speed of 10m/min, beneath a 80 W/cm medium-pressure mercury lamp (Hanovia, USA).The pendulum hardness is then determined in accordance with Konig(DIN53157) in [s]. The pendulum hardness is a measure of thethrough-curing of the composition. The higher the values, the moreeffective the curing which has been carried out. A value of 163 s isachieved. After the first pendulum hardness determination, the sample isafter-exposed under low-pressure mercury lamps of the type TL 40W/03(Philips; emission maximum of 430 nm), and after 15 minutes the pendulumhardness is determined again. Following after exposure, a value of 183 sis obtained. The yellowness index in accordance with ASTMD 5-88 is 4.23.

EXAMPLES 23-25

Instead of the photoinitator compound from example 19, 2 parts of thecompound according to example 5, 20 or 21 are incorporated into aphotocurable formulation as described in example 22, and applied to acoil-coated aluminium sheet as described in example 22. Curing iscarried out by conveying the sample repeatedly on a conveyor belt, whichis moving at a speed of 10 m/min, beneath an 80 W/cm medium-pressuremercury lamp (Hanovia, USA). The sample is then after-exposed underlow-pressure mercury lamps of the TL 40W/03 type (Phillips; emissionmaximum of 430 nm), and after 15 minutes the pendulum hardness isdetermined in accordance with König (DIN53157) in [s] and the yellownessindex is deterance with ASTMD 1925-88. The results are shown in table 4.

TABLE 4 Pendulum Compound Number of hardness Yellowness Ex. from Ex.passages [s] Index 24 5 4 104 1.43 25 20 3 112 1.51 26 21 3 137 1.93

What is claimed is:
 1. A compound of the formula I

in which Ar is a group

 or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy; R₁ and R₂ independently of oneanother are C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; R₃, R₄ and R₅independently of one another are hydrogen, C₁-C₂₀alkyl, OR₁₁ or halogen;or in each case two of the radicals R₁, R₂, R₃, R₄ and R₅ together formC₁-C₂₀alkylene, which can be interrupted by O, S or NR₁₄; R₆ isC₁-C₂₄alkyl, unsubstituted or substituted by cycloalkenyl, phenyl, CN,C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁, N(R₁₄)C(O)N(R₁₄),OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁, SR₁₁, N(R₁₂)(R₁₃)or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃); C₅-C₂₄cycloalkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); C₇-C₂₄arylalkyl which is unsubstituted or substituted onthe aryl group by C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen; C₄-C₂₄cycloalkylwhich is uninterrupted or interrupted once or more than once by O, Sand/or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); or C₈-C₂₄arylcycloalkyl or C₈-C₂₄arylcycloalkenyl; R₁₁ isH, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl, which is interrupted once or more than once by O or S and whichis unsubstituted or is substituted by OH and/or SH; R₁₂ and R₁₃independently of one another are hydrogen, C₁-C₂₀alkyl, C₃-C₈cycloalkyl,phenyl, benzyl or C₂-C₂₀ alkyl which is interrupted once or more thanonce by nonconsecutive O atoms and which is unsubstituted or substitutedby OH and/or SH; or R₁₂ and R₁₃ together are C₃-C₅alkylene which isuninterrupted or interrupted by O, S or NR₁₄; R₁₄ is hydrogen, phenyl,C₁-C₁₂alkyl or C₂-C₁₂alkyl which is interrupted once or more than onceby O or S and which is unsubstituted or substituted by OH and/or SH; andM is hydrogen, Li, Na or K.
 2. A compound of the formula I

in which Ar is a group

R₁ and R₂ independently of one another are C₁-C₈alkyl or OR₁₁; R₃, R₄and R₅ independently of one another are hydrogen or C₁-C₈alkyl; R₆ isC₁-C₁₂alkyl; R₁₁ is H or C₁-C₈alkyl; M is hydrogen or Li.
 3. A processfor the selective preparation of compounds of the formula I according toclaim 1, by (1) reaction of an acyl halide of the formula IV

in which Ar is as defined in claim 1, and X is Cl or Br; with adimetalated organophosphine of the formula V

in which R₆ is as defined in claim 1; and M₁ is Na, Li or K; in themolar ratio 1:1; and (2) where appropriate, subsequent hydrolysis ifcompounds of the formula I in which M is hydrogen are to be obtained. 4.A compound of the formula II

in which A is O or S; x is 0 or 1; Ar is a group

 or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy; R₁ and R₂ independently of oneanother are C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; R₃, R₄ and R₅independently of one another are hydrogen, C₁-C₂₀alkyl, OR₁₁ or halogen;or in each case two of the radicals R₁, R₂, R₃, R₄ and R₅ together formC₁-C₂₀alkylene, which can be interrupted by O, S or NR₁₄; R₆ isC₁-C₂₄alkyl, unsubstituted or substituted by cycloalkenyl, phenyl, CN,C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁, N(R₁₄)C(O)N(R₁₄),OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁, SR₁₁, N(R₁₂)(R₁₃)or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃); C₅-C₂₄cycloalkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); C₇-C₂₄arylalkyl which is unsubstituted or substituted onthe aryl group by C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen; C₄-C₂₄cycloalkylwhich is uninterrupted or interrupted once or more than once by O, Sand/or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); or C₈-C₂₄arylcycloalkyl or C₈-C₂₄arylcycloalkenyl; R₁₁ isH, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl, which is interrupted once or more than once by nonconsecutive Oatoms and which is unsubstituted or substituted by OH and/or SH; R₁₂ andR₁₃ independently of one another are hydrogen, C₁-C₂₀alkyl,C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀ alkyl which is interruptedonce or more than once by O or S and which is unsubstituted orsubstituted by OH and/or SH; or R₁₂ and R₁₃ together are C₃-C₅alkylenewhich is uninterrupted or interrupted by O, S or NR₁₄; Y₁ is C₁-C₁₈alkylwhich is unsubstituted or substituted by one or more phenyl;C₁-C₁₈-halogenoalkyl; C₂-C₁₈alkyl which is interrupted once or more thanonce by O or S and which can be substituted by OH and/or SH;unsubstituted C₃-C₁₈cycloalkyl or C₃-C₁₈cycloalkyl substituted byC₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; C₂-C₁₈alkenyl; or Y₁ is OR₁₁,N(R₁₂)(R₁₃) or one of the radicals

or Y₁ is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy; Y₂ is a direct bond;unsubstituted or phenyl-substituted C₁-C₁₈alkylene; unsubstitutedC₄-C₁₈-cycloalkylene or C₄-C₁₈cycloalkylene substituted by C₁-C₁₂alkyl,OR₁₁, halogen and/or phenyl; unsubstituted C₅-C₁₈cycloalkenylene orC₅-C₁₈cycloalkenylene substituted by C₁-C₁₂alkyl, OR₁₁, halogen and/orphenyl; unsubstituted phenylene or phenylene substituted one to fourtimes by C₁-C₁₂alkyl, OR₁₁, halogen, —(CO)OR₁₄, —(CO)N(R₁₂)(R₁₃) and/orphenyl; or Y₂ is a radical

 where these radicals are unsubstituted or are substituted one to fourtimes on one or both aromatic ring(s) by C₁-C₁₂alkyl, OR₁₁, halogenand/or phenyl; Y₃ is O, S, SO, SO₂, CH₂, C(CH₃)₂, CHCH₃, C(CF₃)₂, (CO),or a direct bond; R₁₄ is hydrogen, phenyl, C₁-C₁₂alkyl or C₂-C₁₂alkylwhich is interrupted once or more than once by O or S and which can besubstituted by OH and/or SH; R₁′ and R₂′ independently of one anotherhave the same meanings as given for R₁ and R₂; and R₃′, R₄′ and R₅′independently of one another have the same meanings as given for R₃, R₄and R₅; or in each case two of the radicals R₁′, R₂′, R₃′, R₄′ and R₅′together form C₁-C₂₀alkylene which may be interrupted by O, S or —NR₁₄;with the proviso that Y₁ is not identical to Ar by reacting analkylacylphosphine compound of formula I according to claim 1 with anacid halide of the formula (IV)

wherein X is Cl or Br; in a molar ratio of about 1:1, optionally in asolvent, at a reaction temperature from about −60° C. to about +120° C.to give a phosphine compound of formula II, wherein x is 0, andoptionally, subsequent oxidation or sulfurization of the resultingphosphine compound to give the corresponding oxide or sulfide compoundwherein x is 1 and A is O or S.
 5. A new process for the preparation ofmonoacylphosphine oxides or sulfides of formula III

in which A is O or S; x is 0 or 1; Ar is a group

 or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or anO-, S- or N-containing 5- or 6-membered heterocyclic ring, where theradicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5-or 6-membered heterocyclic ring are unsubstituted or substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy; R₁ and R₂ independently of oneanother are C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; R₃, R₄ and R₅independently of one another are hydrogen, C₁-C₂₀alkyl, OR₁₁ or halogen;or in each case two of the radicals R₁, R₂, R₃, R₄ and R₅ together formC₁-C₂₀alkylene which can be interrupted by O, S or —NR₁₄; R₆ isC₁-C₂₄alkyl, unsubstituted or substituted by C₅-C₂₄cycloalkenyl, phenyl,CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂, OC(O)R₁₁, OC(O)OR₁₁,N(R₁₄)C(O)N(R₁₄), OC(O)NR₁₄, N(R₁₄)C(O)OR₁₁, cycloalkyl, halogen, OR₁₁,SR₁₁, N(R₁₂)(R₁₃) or

C₂-C₂₄alkyl which is interrupted once or more than once bynonconsecutive O, S or NR₁₄ and which is unsubstituted or substituted byphenyl, OR₁₁, SR₁₁, N(R₁₂)(R₁₃), CN, C(O)R₁₁, C(O)OR₁₁, C(O)N(R₁₄)₂and/or

C₂-C₂₄alkenyl which is uninterrupted or interrupted once or more thanonce by nonconsecutive O, S or NR₁₄ and which is unsubstituted orsubstituted by OR₁₁, SR₁₁ or N(R₁₂)(R₁₃); C₅-C₂₄cycloalkenyl which isuninterrupted or interrupted once or more than once by nonconsecutive O,S or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); C₇-C₂₄arylalkyl which is unsubstituted or substituted onthe aryl group by C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen; C₄-C₂₄cycloalkylwhich is uninterrupted or interrupted once or more than once by O, Sand/or NR₁₄ and which is unsubstituted or substituted by OR₁₁, SR₁₁ orN(R₁₂)(R₁₃); or C₈-C₂₄arylcycloalkyl or C₈-C₂₄arylcycloalkenyl; R₁₁ isH, C₁-C₂₀alkyl, C₂-C₂₀alkenyl, C₃-C₈cycloalkyl, phenyl, benzyl orC₂-C₂₀alkyl which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted by OHand/or SH; R₁₂ and R₁₃ independently of one another are hydrogen,C₁-C₂₀alkyl, C₃-C₈cycloalkyl, phenyl, benzyl or C₂-C₂₀alkyl, which isinterrupted once or more than once by O or S and which is unsubstitutedor substituted by OH and/or SH; or R₁₂ and R₁₃ together areC₃-C₅alkylene which is uninterrupted or interrupted by O, S or NR₁₄; Z₁is C₁-C₂₄alkyl, which is unsubstituted or substituted once or more thanonce by OR₁₅,SR₁₅, N(R₁₆)(R₁₇), phenyl, halogen, CN, —N═C═A,

 or Z₁ is C₂-C₂₄alkyl which is interrupted once or more than once by O,S or NR₁₄ and which can be substituted by OR₁₅, SR₁₅, N(R₁₆)(R₁₇),phenyl, halogen,

 or Z₁ is C₁-C₂₄alkoxy, which is substituted once or more than once byphenyl, CN, —N═C═A,

 or Z₁ is unsubstituted C₃-C₂₄cycloalkyl or C₃-C₂₄cycloalkyl substitutedby C₁-C₂₀alkyl, OR₁₁, CF₃ or halogen; unsubstituted C₂-C₂₄alkenyl orC₂-C₂₄alkenyl substituted by C₆-C₁₂aryl, CN, (CO)OR₁₅ or (CO)N(R₁₈)₂; orZ₁ is C₃-C₂₄cycloalkenyl or is one of the radicals

 or Z₁ is C₁-C₂₄alkylthio, in which the alkyl radical is uninterruptedor interrupted once or more than once by nonconsecutive O or S, and isunsubstituted or substituted by OR₁₅, SR₁₅ and/or halogen; with theproviso that Z₁ and R₆ are not identical; A₁ is O, S or NR_(18a); Z₂ isC₁-C₂₄alkylene; C₂-C₂₄alkylene interrupted once or more than once by O,S, or NR₁₄; C₂-C₂₄alkenylene; C₂-C₂₄alkenylene interrupted once or morethan once by O, S or NR₁₄; C₃-C₂₄cycloalkylene; C₃-C₂₄cycloalkyleneinterrupted once or more than once by O, S or NR₁₄; C₃-C₂₄cycloalkylene;C₃-C₂₄cycloalkenylene interrupted once or more than once by O, S orNR₁₄; where the radicals C₁-C₂₄alkylene, C₂-C₂₄alkylene,C₂-C₂₄alkenylene, C₃-C₂₄cycloalkylene and C₃-C₂₄cycloalkenylene areunsubstituted or are substituted by OR₁₁, SR₁₁, N(R₁₂)(R₁₃)and/orhalogen; or Z₂ is one of the radicals

 where these radicals are unsubstituted or are substituted on thearomatic by C₁-C₂₀alkyl; C₂-C₂₀alkyl which is interrupted once or morethan once by nonconsecutive O atoms and which is unsubstituted orsubstituted by OH and/or SH; OR₁₁, SR₁₁, N(R₁₂)(R₁₃), phenyl, halogen,NO₂, CN, (CO)—OR₁₁, (CO)—R₁₁, (CO)—N(R₁₂)(R₁₃), SO₂R₂₄, OSO₂R₂₄, CF₃and/or CCl₃; or Z₂ is a group

Z₃ is CH₂, CH(OH), CH(CH₃) or C(CH₃)₂; Z₄ is S, O, CH₂, C═O, NR₁₄ or adirect bond; Z₅ is S, O, CH₂, CHCH₃, C(CH₃)₂, C(CF₃)₂, SO, SO₂, CO; Z₆and Z₇ independently of one another are CH₂, CHCH₃ or C(CH₃)₂; r is 0, 1or 2; s is a number from 1 to 12; q is a number from 0 to 50; t and pare each a number from 0 to 20; E, G, G₃ and G₄ independently of oneanother are unsubstituted C₁-C₁₂alkyl or C₁-C₁₂alkyl substituted byhalogen, or are unsubstituted phenyl or phenyl substituted by one ormore C₁-C₄alkyl; or are C₂-C₁₂alkenyl; R_(13a) is C₁-C₂₀alkylsubstituted once or more than once by OR₁₅ or

 or is C₂-C₂₀alkyl which is interrupted once or more than once bynonconsecutive O atoms and is unsubstituted or substituted once or morethan once by OR₁₅, halogen or

 or R_(11a) is C₂-C₂₀alkenyl, C₃-C₁₂alkynyl; or R_(11a) isC₃-C₁₂cycloalkenyl which is substituted once or more than once byhalogen, NO₂, C₁-C₆alkyl, OR₁₁ or C(O)OR,₁₈; or C₇-C₁₆arylalkyl orC₈-C₁₆arylcycloalkyl; R₁₄ is hydrogen, phenyl, C₁-C₁₂alkoxy, C₁-C₁₂alkylor C₂-C₁₂alkyl which is interrupted once or more than once by O or S andwhich is unsubstituted or substituted by OH and/or SH; R₁₅ has one ofthe meanings given for R₁₁ or is a radical

R₁₆ and R₁₇ independently of one another have one of the meanings givenfor R₁₂ or are a radical

R₁₈ is hydrogen, C₁-C₂₄alkyl, C₂-C₁₂alkenyl, C₃-C₈cycloalkyl, phenyl,benzyl; C₂-C₂₀alkyl which is interrupted once or more than once by O orS and which is unsubstituted or substituted by OH; R_(18a) and R_(18b)independently of one another are hydrogen; C₁-C₂₀alkyl, which issubstituted once or more than once by OR₁₅, halogen, styryl,methylstyryl, —N═C═A or

 or C₂-C₂₀alkyl, which is interrupted once or more than once bynonconsecutive O atoms and which is unsubstituted or substituted once ormore than once by OR₁₅, halogen, styryl, methylstyryl or

 or R_(18a) and R_(18b) are C₂-C₁₂alkenyl; C₅-C₁₂cycloalkyl, which issubstituted by —N═C═A or —CH₂—N═C═A and is additionally unsubstituted orsubstituted by one or more C₁-C₄alkyl; or R_(18a) and R_(18b) areC₆-C₁₂aryl, unsubstituted or substituted once or more than once byhalogen, NO₂, C₁-C₆alkyl, C₂-C₄alkenyl, OR₁₁, —N═C═A, —CH₂—N═C═A orC(O)OR₁₈; or R_(18a) and R_(18b) are C₇-C₁₆arylalkyl; or R_(18a) andR_(18b) together are C₈-C₁₆arylcycloalkyl; or R_(18a) and R_(18b)independently of one another are

Y₃ is O, S, SO, SO₂, CH₂, C(CH₃)₂, CHCH₃, C(CF₃)₂, (CO), or a directbond; R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ independently of one another arehydrogen, C₁-C₂₀alkyl; C₂-C₂₀alkyl, which is interrupted once or morethan once by nonconsecutive O atoms and which is unsubstituted orsubstituted by OH and/or SH; or R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are OR₁₁,SR₁₁, N(R₁₂)(R₁₃), NO₂, CN, SO₂R₂₄, OSO₂R₂₄, CF₃, CCl₃, halogen; orphenyl which is unsubstituted or substituted once or more than once byC₁-C₄alkyl or C₁-C₄alkoxy; or in each case two of the radicals R₁₉, R₂₀,R₂₁, R₂₂ and R₂₃ together form C₁-C₂₀alkylene which is uninterrupted orinterrupted by O, S or —NR₁₄; R₂₄ is C₁-C₁₂alkyl, halogen-substitutedC₁-C₁₂alkyl, phenyl, or phenyl substituted by OR₁₁ and/or SR₁₁; with theproviso that R₆ and Z₁ are not identical; by reacting analkylacylphosphine compound of formula I according to claim 1 with ahalide of the formula (VI) Z₁—X  (VI), wherein X is Cl or Br; in a molarratio of about 1:1, optionally in a solvent, at a reaction temperaturefrom about −60° C. to about +120° C. to give a phosphine compound offormula III wherein x is 0, and optionally, subsequent oxidation orsulfurization of the resulting phosphine compound to give thecorresponding oxide or sulfide compound wherein x is 1 and A is O or S.